Positive-electrode active material precursor for nonaqueous electrolyte secondary battery and method for manufacturing positive-electrode active material precursor for nonaqueous electrolyte secondary battery

ABSTRACT

A positive-electrode active material precursor for a nonaqueous electrolyte secondary battery is provided that includes a nickel-cobalt-manganese carbonate composite represented by general formula Ni x Co y Mn z M t CO 3  (where x+y+z+t=1, 0.05≤x≤0.3, 0.1≤y≤0.4, 0.55≤z≤0.8, 0≤t≤0.1, and M denotes at least one additional element selected from a group consisting of Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo, and W) and a hydrogen-containing functional group, wherein H/Me representing the ratio of the amount of hydrogen to the amount of metal components Me included in the positive-electrode active material precursor is greater than or equal to 1.60.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a divisional application of and claims the benefitof priority under 35 U.S.C. 120 to patent application Ser. No.16/066,445 filed on Jan. 5, 2017, which has effectively entered under 35U.S.C. 371 (c) the national stage on Jun. 27, 2018, from the PCTApplication No. PCT/JP2017/000148, which claims priority to JapanesePatent Application No. 2016-001366, filed on Jan. 6, 2016, and JapanesePatent Application No. 2016-186242, filed on Sep. 23, 2016. The contentsof these applications are incorporated herein by reference in theirentirety.

TECHNICAL FIELD

The present invention relates to a positive-electrode active materialprecursor for a nonaqueous electrolyte secondary battery and a methodfor manufacturing a positive-electrode active material precursor for anonaqueous electrolyte secondary battery.

BACKGROUND ART

In recent years, with the widespread use of portable electronic devices,such as mobile phones and notebook computers, there is a high demand forthe development of small and light nonaqueous electrolyte secondarybatteries having high energy density. There is also a high demand forthe development of high-output secondary batteries as large batteriesfor motor drive power sources.

Lithium ion batteries are secondary batteries that can meet theserequirements. A lithium ion secondary battery includes a negativeelectrode, a positive electrode, an electrolytic solution, and the like.Materials capable of sustaining lithium insertion and deinsertion areused as a negative-electrode active material and a positive-electrodeactive material.

Lithium ion batteries are currently the subject of substantial researchand development. In particular, a lithium ion secondary battery using alayered or spinel type lithium metal composite oxide as apositive-electrode material can achieve a high voltage of around 4V andis therefore being developed for practical applications as a batteryhaving high energy density.

Various lithium composite oxides have been proposed for use as thepositive-electrode material of such a lithium ion secondary battery. Forexample, lithium-cobalt composite oxide (LiCoO₂), which is relativelyeasy to synthesize; lithium-nickel composite oxide (LiNiO₂) using nickelas a cheaper alternative to cobalt; lithium-nickel-cobalt-manganesecomposite oxide (LiNi_(1/3)Col_(1/3)Mn_(1/3)O₂), lithium-manganesecomposite oxide (LiMn₂O₄) using manganese, lithium-nickel-manganesecomposite oxide (LiNi_(0.5)Mn_(0.5)O₂); lithium-richnickel-cobalt-manganese composite oxide (Li₂MnO₃—LiNi_(x)Mn_(y)Co_(z)O₂)and the like have been proposed.

Among these positive electrode active materials, lithium-richnickel-cobalt-manganese composite oxide is attracting attention as amaterial having high capacity and excellent thermal stability. Thelithium-rich nickel-cobalt-manganese composite oxide is a layeredcompound like lithium-cobalt composite oxide and lithium-nickelcomposite oxide (e.g., see Non-Patent Literature Document 1).

Methods for manufacturing a precursor for obtaining such lithium-richnickel-cobalt-manganese composite oxide are disclosed in Patent Document1 and Patent Document 2, for example.

PRIOR ART DOCUMENTS Patent Documents

-   Patent Document 1: Japanese Unexamined Patent Application    Publication No. 2011-028999-   Patent Document 2: Japanese Unexamined Patent Application    Publication No. 2011-146392

NON-PATENT LITERATURE DOCUMENTS

-   Non-Patent Literature Document 1: “R&D of Solid Solution Cathode    Materials for Lithium Ion Batteries”, FB TECHNICAL NEWS, No. 66,    January 2011, pp. 3-10

SUMMARY OF THE INVENTION Problem to be Solved by the Invention

An effective measure for increasing the output of a lithium ionsecondary battery includes reducing the moving distance between thepositive electrode and the negative electrode of the lithium ion cell.As such, it is advantageous to use a positive-electrode materialincluding porous particles having uniform pores within the particles.

Although Patent Documents 1 and 2 describe methods for manufacturing aprecursor and the composition of the positive electrode active materialthat is manufactured using the precursor, the above documents make noreference to the particle structure of the positive electrode activematerial and the internal structure of secondary particles.

In view of the above problems of the prior art, one aspect of thepresent invention is directed to providing a positive electrode activematerial precursor for a nonaqueous electrolyte secondary battery thatis capable of forming a positive electrode active material for thenonaqueous electrolyte secondary battery containing porous particles.

Means for Solving the Problem

According to one embodiment of the present invention, apositive-electrode active material precursor for a nonaqueouselectrolyte secondary battery is provided that includes anickel-cobalt-manganese carbonate composite represented by generalformula Ni_(x)Co_(y)Mn_(z)M_(t)CO₃ (where x+y+z+t=1, 0.05≤x≤0.3,0.55≤z≤0.8, 0≤t≤0.1, and M denotes at least one additional elementselected from a group consisting of Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo,and W), and a hydrogen-containing functional group, wherein H/Merepresenting the ratio of the amount of hydrogen H to the amount ofmetal components Me included in the positive-electrode active materialprecursor is greater than or equal to 1.60.

Advantageous Effect of the Invention

According to an aspect of the present invention, a positive-electrodeactive material precursor for a nonaqueous electrolyte secondary batterymay be provided that is capable of forming a positive-electrode activematerial for a nonaqueous electrolyte secondary battery containingporous particles.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flowchart showing a method for manufacturing apositive-electrode active material precursor for a nonaqueouselectrolyte secondary battery according to an embodiment of the presentinvention;

FIG. 2 is a SEM image of a precursor obtained in Example 1 of thepresent invention;

FIG. 3A is a SEM image of a positive-electrode active material obtainedin Example 1 of the present invention;

FIG. 3B is a partially enlarged view of FIG. 3A;

FIG. 4 is a cross-sectional view of a coin battery manufactured inExample 1 of the present invention;

FIG. 5A is a SEM image of a positive-electrode active material obtainedin Comparative Example 2; and

FIG. 5B is a partially enlarged view of FIG. 5A.

EMBODIMENTS FOR IMPLEMENTING THE INVENTION

In the following, embodiments of the present invention are describedwith reference to the accompanying drawings. Note that the presentinvention is by no way limited to the embodiments described below andvarious modifications and substitutions may be made with respect to theembodiments described below without departing from the scope of thepresent invention.

[Positive-Electrode Active Material Precursor for Nonaqueous ElectrolyteSecondary Battery]

In the following, an example configuration of a positive-electrodeactive material precursor for a nonaqueous electrolyte secondary batteryaccording to an embodiment of the present invention will be described.

The positive electrode active material precursor for a nonaqueouselectrolyte secondary battery according to the present embodiment mayinclude a nickel-cobalt-manganese carbonate composite that isrepresented by the general formula Ni_(x)Co_(y)Mn_(z)M_(t)CO₃ (wherex+y+z+t=1, 0.05≤x≤0.3, 0.1≤y≤0.4, 0.55≤z≤0.8, 0≤t≤0.1, and M denotes atleast one additional element selected from a group consisting of Mg, Ca,Al, Ti, V, Cr, Zr, Nb, Mo, and W), and a hydrogen-containing functionalgroup.

Further, H/Me representing the ratio of the amount of hydrogen H to theamount of metal components Me included in the positive-electrode activematerial precursor may be controlled to be greater than or equal to1.60.

As described above, the positive electrode active material precursor fora nonaqueous electrolyte secondary battery according to the presentembodiment (hereinafter also simply referred to as “precursor”) mayinclude a nickel-cobalt-manganese carbonate composite and ahydrogen-containing functional group. Note that the precursor mayconsist of the nickel-cobalt-manganese carbonate composite and thehydrogen-containing functional group.

The precursor according to the present embodiment may includesubstantially spherical secondary particles formed by aggregating aplurality of fine primary particles. The precursor may also consist ofsuch secondary particles.

The precursor according to the present embodiment including thenickel-cobalt-manganese carbonate composite and the hydrogen-containingfunctional group has high particle size uniformity and fine crystals,and as such, the precursor according to the present embodiment may beused as a raw material (i.e., precursor) of a positive-electrode activematerial for a nonaqueous electrolyte secondary battery.

The precursor according to the present embodiment will be specificallydescribed below.

(Composition)

As described above, the nickel-cobalt-manganese carbonate composite is anickel-cobalt-manganese composite in basic carbonate form represented bythe general formula: Ni_(x)Co_(y)Mn_(z)M_(t)CO₃.

In the above general formula, x+y+z+t=1, 0.05≤x≤0.3, 0.1≤y≤0.4,0.55≤z≤0.8, 0≤t≤0.1, and M denotes at least one additional elementselected from a group consisting of Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo,and W.

Note that the precursor according to the present embodiment may includecompounds with indeterminate compositions containing carbonates andhydroxides that may be represented by general formula 1:xMn₂(CO₃)₃.yMn(OH)₃; general formula 2: xCo(CO₃)₂.yCo(OH)₂.zH₂O; generalformula 3: Ni₄CO₃(OH)₆(H₂O)₄; and the like that are collectivelyrepresented by the above-described general formula.

When the precursor according to the present embodiment is used as aprecursor of a positive-electrode active material for a nonaqueouselectrolyte secondary battery, at least one additional element may beadded to the nickel-cobalt-manganese carbonate composite as describedabove in order to further improve battery characteristics, such as cyclecharacteristics and output characteristics.

The at least one additional element selected from the group consistingof Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo, and W may be contained in thenickel-cobalt-manganese carbonate composite at a predetermined atomnumber ratio t, and is preferably uniformly distributed inside secondaryparticles and/or uniformly coated on the surfaces of the secondaryparticles.

Note that when the atom number ratio t of the additional element in thenickel-cobalt-manganese carbonate composite exceeds 0.1, metal elementscontributing to oxidation-reduction reactions (redox reactions) maypotentially be reduced and the battery capacity may potentiallydecrease.

Even when the nickel-cobalt-manganese carbonate composite does notcontain an additional element, the positive-electrode active materialmanufactured using the precursor according to the present embodiment mayhave satisfactory battery characteristics, such as cycle characteristicsand output characteristics. As such, the nickel-cobalt-manganesecarbonate composite does not have to contain an additional element.

Thus, the atom number ratio t of the additional element is preferablyadjusted to be 00.1.

As described above, the additional element may be at least one elementselected from the group consisting of Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo,and W, and in particular, the additional element preferably includesmolybdenum (Mo). That is, the additional element M in the above generalformula: Ni_(x)Co_(y)Mn_(z)M_(t)CO₃ preferably includes Mo. According tostudies conducted by the inventors of the present invention, the initialdischarge capacity of a nonaqueous electrolyte secondary battery can beparticularly increased when the nonaqueous electrolyte secondary batteryuses a positive-electrode active material prepared using a precursorcontaining an additional element including molybdenum.

Further, the content ratio of molybdenum in the metal components Ni, Co,Mn, and the additional element M of the nickel-cobalt-manganesecarbonate composite is preferably adjusted so that molybdenumconstitutes at least 0.5 at % and no more than 5.0 at % of the metalcomponents. By adjusting the content ratio of molybdenum in the metalcomponents of the nickel-cobalt-manganese carbonate composite to begreater than or equal to 0.5 at %, the effect of increasing the initialdischarge capacity of the nonaqueous electrolyte secondary battery asdescribed above can be particularly enhanced. Also, note that molybdenumhas an effect of promoting sintering during a firing process. In thisrespect, by adjusting the content ratio of molybdenum in the metalcomponents of the nickel-cobalt-manganese carbonate composite to be lessthan or equal to 5 at %, the generation of excessively large crystalscan be prevented, and an increase in resistance and a decrease indischarge capacity of a battery manufactured using the precursor can beprevented.

Further, studies conducted by the inventors of the present inventionrevealed that by including molybdenum in the additional element, thespecific surface area of the positive-electrode active material preparedusing the precursor can be reduced. That is, fine pores in thepositive-electrode active material can be structurally changed intolarger pores by adding molybdenum. Further, studies conducted by theinventors of the present invention revealed that by arranging thespecific surface area of the positive-electrode active material to begreater than or equal to 1.5 m²/g and less than or equal to 15.0 m²/g, apositive-electrode mixed material paste may be easily manufactured.Thus, molybdenum is preferably included in the additional element alsofrom the perspective of controlling the specific surface area of thepositive-electrode active material to be within the above range.

Also, preferably, the additional element is uniformly distributed insidethe secondary particles included in the precursor (hereinafter alsosimply referred to as “precursor particles”) and/or uniformly coated onthe surfaces of the secondary particles.

Note that the state of the additional element in thenickel-cobalt-manganese carbonate composite is not particularly limited.However, preferably, the additional element is uniformly distributedinside and/or uniformly coated on the surface of thenickel-cobalt-manganese carbonate composite as described above. That is,when the precursor according to the present embodiment is used as aprecursor of a positive-electrode active material, batterycharacteristics can be particularly improved by having the additionalelement uniformly distributed inside and/or uniformly coated(distributed) on the surface of the nickel-cobalt-manganese carbonatecomposite.

Note that in order to sufficiently enhance the effect of improvingbattery characteristics even when the amount of the at least oneadditional element contained in the nickel-cobalt-manganese carbonatecomposite is substantially small, the at least one additional element ispreferably distributed at a higher concentration on the surface of thecarbonate composite as compared with the concentration inside thecarbonate composite.

As described above, even when the amount of the at least one additionalelement contained in the nickel-cobalt-manganese carbonate composite issubstantially small, battery characteristics can be improved and adecrease in the battery capacity can be prevented.

Also, the precursor according to the present embodiment may include thehydrogen-containing functional group as described above. Examples of thehydrogen-containing functional group include a hydrogen group, ahydroxyl group, and the like. The hydrogen-containing functional groupis mixed into the precursor during the manufacturing process. Theprecursor according to the present embodiment is preferably adjusted sothat H/Me representing the ratio of the amount of hydrogen H to theamount of metal components Me contained in the precursor is greater thanor equal to 1.60. In this way, the positive-electrode active materialmanufactured using the precursor may be made of porous particles.

Note that the metal components Me contained in the precursor includesNi, Co, Mn and the additional element M that are represented in theabove general formula.

Also, note that while the precursor according to the present embodimentmay contain a component other than the nickel-cobalt-manganese carbonatecomposite and the hydrogen-containing functional group, the precursoraccording to the present embodiment may also consist of thenickel-cobalt-manganese carbonate composite and the hydrogen-containingfunctional group. Note that even when the precursor of according to thepresent embodiment consists of the nickel-cobalt-manganese carbonatecomposite and the hydrogen-containing functional group, the presentembodiment does not exclude the inevitable inclusion of other componentsduring the manufacturing process and the like.

[Method for Manufacturing Positive-Electrode Active Material Precursorfor Nonaqueous Electrolyte Secondary Battery]

In the following, an example method for manufacturing apositive-electrode active material precursor for a nonaqueouselectrolyte secondary battery (hereinafter also simply referred to as“precursor manufacturing method”) according to an embodiment of thepresent invention will be described.

Note that the precursor manufacturing method according to the presentembodiment may be implemented to manufacture the above-describedprecursor, and as such, aspects of the precursor manufacturing methodaccording to the present embodiment that have already been describedabove in connection with the precursor may be omitted in the descriptionbelow.

In the precursor manufacturing method according to the presentembodiment, a precursor can be obtained by a crystallization reaction,and the obtained precursor can be washed and dried as necessary.

Specifically, the precursor manufacturing method according to thepresent embodiment is a method for manufacturing a positive-electrodeactive material precursor for a nonaqueous electrolyte secondary batterythat includes a nickel-cobalt-manganese carbonate composite representedby general formula Ni_(x)Co_(y)Mn_(z)M_(t)CO₃ (where x+y+z+t=1,0.05≤x≤0.3, 0.1≤y≤0.4, 0.55≤z≤0.8, and M denotes at least one additionalelement selected from a group consisting of Mg, Ca, Al, Ti, V, Cr, Zr,Nb, Mo, and W), and a hydrogen-containing functional group. Theprecursor manufacturing method may include the following steps.

A nucleation step of forming nuclei in a mixed aqueous solution that isprepared by mixing together, under the presence of carbonate ions, aninitial aqueous solution containing an alkaline substance and/or anammonium ion supplier, an aqueous solution containing nickel as a metalcomponent, an aqueous solution containing cobalt as a metal component,and an aqueous solution containing manganese as a metal component.

A particle growth step of growing the nuclei formed in the nucleationstep.

The nucleation step may be performed under an oxygen-containingatmosphere while controlling the pH value of the mixed aqueous solutionto be less than or equal to 7.5 at a reaction temperature of 40° C. asthe standard temperature.

The example flow of the precursor manufacturing method according to thepresent embodiment as illustrated in FIG. 1 will be described below. InFIG. 1, the precursor manufacturing method according to the presentembodiment includes: (A) a nucleation step; and (B) a particle growthstep of growing the particles of the precursor using the coprecipitationmethod after performing the nucleation step.

In the continuous crystallization method, which is conventionally used,nucleation reaction and particle growth reaction proceed simultaneouslyin the same reaction tank, and as such, the obtained compound particleshave a wide particle size distribution.

In contrast, the precursor manufacturing method according to the presentembodiment clearly separates the time during which nucleation reactionmainly occurs (nucleation step) and the time during which particlegrowth reaction mainly occurs (particle growth step). In this way,precursor particles having a narrow particle size distribution may beobtained even if both steps are performed in the same reaction tank.Note that the precursor manufacturing step according to the presentembodiment may further include a nucleus disintegration step that isperformed between the above two steps, the nucleus disintegration stepinvolving stopping the addition of raw materials and only performingstirring.

In the following, each step of the precursor manufacturing methodaccording to the present embodiment will be described in detail.

(1) Nucleation Step

The nucleation step will be described with reference to FIG. 1.

As shown in FIG. 1, in the nucleation step, first, ion exchange water(water) and an alkaline substance and/or an ammonium ion supplier may bemixed together in a reaction tank to prepare an initial aqueoussolution.

The ammonium ion supplier is not particularly limited but is preferablyat least one type of aqueous solution selected from a group consistingof ammonium carbonate aqueous solution, ammonia water, ammonium chlorideaqueous solution, and ammonium sulfate aqueous solution.

Also, the alkaline substance is not particularly limited but ispreferably at least one type of substance selected from a groupconsisting of sodium carbonate, sodium hydrogen carbonate, potassiumcarbonate, sodium hydroxide, and potassium hydroxide.

In the nucleation step, the pH value of a mixed aqueous solution that isobtained by adding aqueous solutions containing metal components, suchas an aqueous solution containing nickel as a metal component, to theinitial aqueous solution is preferably maintained at a lower pH valuethan that during the particle growth step (described below). Bymaintaining the pH value of the mixed aqueous solution at a lower value,nuclei in the mixed aqueous solution can be reduced in size andincreased in number so that the particle size of the secondary particlescontained in the obtained precursor can be reduced.

In this respect, preferably, an acidic substance is added to the initialaqueous solution as necessary to adjust the pH value to be greater thanor equal to 5.4 and less than or equal to 7.5, and more preferablygreater than or equal to 6.4 and less than or equal to 7.4. Inparticular, the pH value of the initial aqueous solutions is morepreferably adjusted to be greater than or equal to 6.4 and less than orequal to 7.0.

The pH value of the mixed aqueous solution is also preferably maintainedto be within the above range during the nucleation step. Note thatbecause the pH value of the mixed aqueous solution fluctuates slightlyduring the nucleation step, the maximum value of the pH value of themixed aqueous solution during the nucleation step may be regarded as thepH value of the mixed aqueous solution during the nucleation step, andsuch pH value of the mixed aqueous solution is preferably adjusted to bewithin the above range.

The acidic substance is not particularly limited but sulfuric acid orthe like may be preferably used, for example. The acidic substance ispreferably the same type of acid as that of the metal salt used inpreparing the aqueous solution containing metal components to be addedto the initial aqueous solution.

Note that during the nucleation step, the pH value of the mixed aqueoussolution is preferably controlled to be no more than 0.2 above or belowa center value (set pH value).

In the nucleation step, by blowing an oxygen-containing gas into thereaction tank in which the initial aqueous solution is prepared tocontrol the atmosphere within the reaction tank, the aqueous solutionscontaining metal components such as the aqueous solution containingnickel may be supplied to the reaction tank at a constant flow rate, andthe pH value of the mixed aqueous solution may be controlled to bewithin a predetermined range. In this way, dissolved oxygen contained inthe mixed aqueous solution and oxygen contained in the oxygen-containinggas supplied to the reaction tank may promote a reaction to formamorphous fine particles of carbonate that are not single crystals ofcarbonate. Also, by blowing an oxygen-containing gas into the reactiontank, the hydrogen-containing functional group may be more easily mixedinto the precursor as compared with the case of performing thenucleation step in an inert gas atmosphere, and H/Me representing theratio of the amount of hydrogen H and the amount of metal components Mecontained in the obtained precursor can be controlled to be greater thanor equal to 1.60.

Note that in the nucleation step, the oxygen-containing gas may continueto be supplied into the reaction tank even while the aqueous solutionscontaining metal components such as the aqueous solution containingnickel are added to the initial aqueous solution.

In the case of supplying an oxygen-containing gas into the reactiontank, the amount of the oxygen-containing gas to be supplied can bedetermined by measuring the concentration of dissolved oxygen in themixed aqueous solution. Because dissolved oxygen in the mixed aqueoussolution is consumed during the nucleation step, the amount of dissolvedoxygen/oxygen supplied may be deemed sufficient for causing a reactionif the amount of dissolved oxygen in the mixed aqueous solution is atleast half the saturation amount.

Note that air or the like may be used as the oxygen-containing gas, forexample.

In the nucleation step, the mixed aqueous solution may be formed byadding and mixing an aqueous solution containing nickel as a metalcomponent, an aqueous solution containing cobalt as a metal component,and an aqueous solution containing manganese as a metal component intothe initial aqueous solution in the reaction tank.

When adding the aqueous solutions containing metal components such asthe aqueous solution containing nickel to the initial aqueous solution,the pH value of the mixed aqueous solution to be obtained is preferablycontrolled to be less than or equal to 7.5 at a reaction temperature of40° C. as the standard temperature. The pH value is more preferablycontrolled to be less than or equal to 7.4, and still more preferablyless than or equal to 7.0. In this respect, preferably, the aqueoussolution containing a metal component, such as the aqueous solutioncontaining nickel, is gradually added dropwise into the initial aqueoussolution rather than being added at once.

Also, in order to control the pH value of the mixed aqueous solution,when dropping the aqueous solutions containing metal components such asthe aqueous solution containing nickel, a pH adjustment aqueous solutionmay also be dropped into the initial aqueous solution along with theaqueous solutions containing metal components. The pH adjustment aqueoussolution to be used is not particularly limited, but for example, anaqueous solution containing an alkaline substance and/or an ammonium ionsupplier may be used. Note that the alkaline substance and the ammoniumion supplier are not particularly limited, but the same substances asthose described in the initial aqueous solution can be used, forexample. The method of supplying the pH adjustment aqueous solution intothe reaction tank is not particularly limited, but for example, whilestirring the obtained mixed aqueous solution, the pH adjustment aqueoussolution may be added using a pump capable of flow rate control, such asa metering pump, so that the pH value can be maintained within apredetermined range.

Then, particles that constitute nuclei of the precursor are formed inthe mixed aqueous solution obtained by adding the aqueous solutionscontaining metal components such as the aqueous solution containingnickel to the initial aqueous solution as described above. Note thatwhether a predetermined amount of nuclei has been formed in the mixedaqueous solution can be determined based on the amount of metal saltcontained in the mixed aqueous solution.

In the following, the aqueous solution containing nickel as a metalcomponent, the aqueous solution containing cobalt as a metal component,and the aqueous solution containing manganese as a metal component thatare added to the initial aqueous solution in the nucleation step will bedescribed.

The aqueous solution containing nickel as a metal component, the aqueoussolution containing cobalt as a metal component, and the aqueoussolution containing manganese as a metal component may each contain ametal compound including the corresponding metal component. That is, forexample, the aqueous solution containing cobalt as a metal component maycontain a metal compound including cobalt.

As the metal compound, a water-soluble metal compound is preferablyused, and examples of the water-soluble metal compound include nitrates,sulfates, hydrochlorides and the like. Specifically, for example, nickelsulfate, cobalt sulfate, manganese sulfate or the like can be suitablyused.

The aqueous solution containing nickel as a metal component, the aqueoussolution containing cobalt as a metal component, and the aqueoussolution containing manganese as a metal component may be mixedtogether, in part or entirely, to form a metal component-containingmixed aqueous solution, and the resulting metal component-containingmixed aqueous solution may be added to the initial aqueous solution.

The composition ratios of the respective metals in the obtainedprecursor will be the same as the composition ratios of the respectivemetals in the metal component-containing mixed aqueous solution. Assuch, for example, the metal component-containing mixed aqueous solutionis preferably prepared by adjusting the ratios of the respective metalcompounds to be dissolved in the aqueous solution so that thecomposition ratios of the respective metals contained in the metalcomponent-containing mixed aqueous solution to be added to the initialaqueous solution in the nucleation step can be controlled to be equal tothe composition ratios of the respective metals in the precursor to beproduced.

Note that in the case where certain metal compounds may react with eachother to produce an unnecessary compound when a plurality of metalcompounds are mixed together, the aqueous solutions containing therespective metal components may be simultaneously added to the initialaqueous solution at predetermined ratios.

When the aqueous solutions containing the respective metal componentsare not mixed together and are separately added to the initial aqueoussolution, the aqueous solutions containing the respective metalcomponents are preferably prepared by controlling the composition ratiosof the respective metals in the entire aqueous solution containing therespective metal components to be added to be equal to the compositionratios of the respective metals in the precursor to be produced.

As described above, the precursor to be manufactured by the precursormanufacturing method according to the present embodiment may include anickel-cobalt-manganese carbonate composite represented by generalformula Ni_(x)Co_(y)Mn_(z)M_(t)CO₃ (where x+y+z+t=1, 0.05≤x≤0.3,0.1≤y≤0.4, 0.55≤z≤0.8, 0≤t≤0.1, and M denotes at least one additionalelement selected from a group consisting of Mg, Ca, Al, Ti, V, Cr, Zr,Nb, Mo, and W), and a hydrogen-containing functional group.

That is, the precursor may further include an additional element otherthan nickel, cobalt, and manganese.

As such, in the nucleation step, an aqueous solution (hereinafter alsosimply referred to as “additional-element-containing aqueous solution”)containing at least one additional element selected from the groupconsisting of Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo, and W (hereinafter alsosimply referred to as “additional element”) may also be added to theinitial aqueous solution. As described above, the additional elementpreferably contains Mo, and as such, an aqueous solution containing atleast molybdenum as a metal component is preferably used as theaqueous-solution-containing aqueous solution.

Note that in the case where aqueous solutions containing metalcompounds, such as the aqueous solution containing nickel as the metalcomponent and the like, are mixed together to prepare a metalcomponent-containing mixed aqueous solution to be added to the initialaqueous solution, the additional-element-containing aqueous solution mayalso be added to and mixed with the metal component-containing mixedaqueous solution.

Also, in the case where aqueous solutions containing metal compounds,such as the aqueous solution containing nickel and the like, are notmixed together and are separately added to the initial aqueous solution,the additional-element-containing aqueous solution may also beseparately added to the initial aqueous solution along with the aqueoussolutions containing metal components.

The additional-element-containing aqueous solution may be preparedusing, for example, a compound containing the additional element.Examples of the compound containing the additional element includetitanium sulfate, ammonium peroxotitanate, potassium titanium oxalate,vanadium sulfate, ammonium vanadate, chromium sulfate, potassiumchromate, zirconium sulfate, zirconium nitrate, niobium oxalate,ammonium molybdenum acid, sodium tungstate, ammonium tungstate, and thelike. The compound to be added can be selected according to theadditional element to be added.

As described above, the additional element is preferably uniformlydistributed within the nucleus particles contained in the precursorand/or uniformly coated on the surfaces of the nucleus particlescontained in the precursor.

By adding the above-described additional-element-containing aqueoussolution to the mixed aqueous solution, the additional element can beuniformly dispersed within the nucleus particles contained in theprecursor.

Further, in order to uniformly coat the additional element on thesurfaces of the secondary particles of the precursor, for example, acoating step of coating the surfaces with the additional element may beperformed after the particle growth step (described below) is completed.The coating step will be described below in connection with the particlegrowth step.

In the nucleation step, an aqueous solution containing nickel as a metalcomponent and the like may be added to and mixed with an initial aqueoussolution under the presence of carbonate ions to form a mixed aqueoussolution so that nuclei may be formed in the mixed aqueous solution.Note that the method of supplying carbonate ions in the above step isnot particularly limited, but for example, the carbonate ions may besupplied to the mixed aqueous solution by supplying carbon dioxide intothe reaction tank together with the oxygen-containing gas as describedbelow. The carbonate ions may also be supplied using a carbonate saltwhen preparing the initial aqueous solution or the pH adjustment aqueoussolution, for example.

As described above, in the nucleation step, an aqueous solutioncontaining nickel as a metal component and the like may be added to andmixed with an initial aqueous solution under the presence of carbonateions to form a mixed aqueous solution so that nuclei may be formed inthe mixed aqueous solution.

In this case, the concentration of metal compounds in the mixed aqueoussolution is preferably greater than or equal to 1 mol/L and less than orequal to 2.6 mol/L, and more preferably greater than or equal to 1.5mol/L and less than or equal to 2.2 mol/L.

This is because when the concentration of the metal compounds in themixed aqueous solution is less than 1 mol/L, the amount ofcrystallization per reaction tank is reduced such that productivity isdecreased. On the other hand, when the concentration of the metalcompounds in the mixed aqueous solution exceeds 2.6 mol/L, theconcentration of the metal compounds may exceed the saturationconcentration at ordinary temperature such that crystals may bereprecipitated and clog the piping of equipment, for example.

Note that the concentration of the metal compounds refers to theconcentration of the metal compounds derived from the aqueous solutionsadded to the mixed aqueous solution, including the aqueous solutioncontaining nickel as a metal component, the aqueous solution containingcobalt as a metal component, the aqueous solution containing manganeseas a metal component, and, in some cases, theadditional-element-containing aqueous solution.

In the nucleation step, the temperature of the mixed aqueous solution ispreferably maintained to be greater than or equal to 20° C., and or morepreferably greater than or equal to 30° C. Note that although the upperlimit for the temperature of the mixed aqueous solution in thenucleation step is not particularly limited, for example, thetemperature is preferably maintained to be less than or equal to 70° C.,and or more preferably less than or equal to 50° C.

This is because when the temperature of the mixed aqueous solution inthe nucleation step is less than 20° C., nucleation may easily occur dueto low solubility of the mixed aqueous solution such thatcontrollability may be compromised.

On the other hand, when the temperature of the mixed aqueous solution inthe nucleation step exceeds 70° C., distortion may occur in primarycrystals and tap density may be decreased.

In the nucleation step, the ammonium ion concentration in the mixedaqueous solution is not particularly limited, but for example, theammonium ion concentration is preferably greater than or equal to 0 g/Land less than or equal to 20 g/L, and is more preferably maintained at aconstant value.

Note that the pH value in the mixed aqueous solution, the ammonium ionconcentration, the amount of dissolved oxygen, and the like may bemeasured by a general pH meter, an ion meter, a dissolved oxygen meter,respectively.

After completing the nucleation step, i.e., after adding the metalcomponent-containing mixed aqueous solution and the like to the initialaqueous solution, stirring of the mixed aqueous solution is continuedand a process of disintegrating the generated nuclei is preferablyperformed (nucleus disintegration step). In the case of performing thenucleus disintegration step, the process is preferably performed for atleast 1 minute, and more preferably for at least 3 minutes. Byperforming the nucleus disintegration step, aggregation of the generatednuclei, enlargement of the particle diameter, and density decrease ofthe particles may be more reliably prevented.

(2) Particle Growth Step

In the following, the particle growth step will be described withreference to FIG. 1.

In the particle growth step, nuclei generated in the nucleation step canbe grown.

Specifically, for example, as shown in FIG. 1, in the particle growthstep, the pH value of the mixed aqueous solution obtained in thenucleation step can be adjusted.

For example, the pH value of the mixed aqueous solution may be adjustedto be greater than or equal to 6.0 and less than or equal to 9.0 at areaction temperature of 40° C. as the standard temperature. The pH valueof the mixed aqueous solution is more preferably adjusted to be greaterthan or equal to 6.4 and less than or equal to 8.0, and more preferablygreater than or equal to 7.1 and less than or equal to 8.0. The pH valueof the mixed aqueous solution can be adjusted by adding a pH adjustmentsolution as described below, for example.

Note that by adjusting the pH value of the mixed aqueous solution to begreater than or equal to 6.0 and less than or equal to 9.0, cationimpurities may be prevented from remaining in the mixed aqueoussolution.

The particle growth step may include a step of adding and mixing anaqueous solution containing nickel as a metal component, an aqueoussolution containing cobalt as a metal component, and an aqueous solutioncontaining manganese as a metal component into the mixed aqueoussolution obtained after the nucleation step, under the presence ofcarbonate ions.

Note that the mixed aqueous solution obtained after the nucleation stepis preferably a pH value-adjusted mixed aqueous solution that hasundergone pH adjustment after the nucleation step as described above.

Also, the aqueous solution containing nickel as a metal component, theaqueous solution containing cobalt as a metal component, and the aqueoussolution containing manganese as a metal component may be mixedtogether, in part or entirely, in the same manner as in the nucleationstep, to form a metal component-containing mixed aqueous solution, andthe resulting metal component-containing mixed aqueous solution may beadded to the mixed aqueous solution. In the case where certain metalcompounds may react with each other to produce an unnecessary compoundwhen a plurality of metal compounds are mixed together, the aqueoussolutions containing the respective metal components may be separatelyadded to the mixed aqueous solution.

Further, when adding the aqueous solution containing nickel as a metalcomponent and the like to the mixed aqueous solution, an additionalelement-containing aqueous solution may also be added along with theaqueous solutions containing metal components as in the nucleation step.Also, the additional element-containing aqueous solution may be added toand mixed with the metal component-containing mixed aqueous solution asdescribed above. Also, in the case where the aqueous solutionscontaining the respective metal components are separately added to themixed aqueous solution, the additional element-containing aqueoussolution may also be separately added to the mixed aqueous solution.

The aqueous solution containing nickel as a metal component, the aqueoussolution containing cobalt as a metal component, and the aqueoussolution containing manganese as a metal component that are used in theparticle growth step may be the same aqueous solutions as those used inthe nucleation step. Also, concentration adjustment and the like may beseparately performed on the aqueous solutions containing the respectivemetal components, for example.

When adding the aqueous solution containing nickel as a metal componentand the like to the mixed aqueous solution, the pH value of the obtainedmixed aqueous solution is preferably controlled to be within apredetermined range as described below. In this respect, the aqueoussolution containing nickel as a metal component and the like may begradually added dropwise into the mixed aqueous solution rather thanbeing added at once. For example, the aqueous solutions containing themetal components or the metal component-containing mixed aqueoussolution may be supplied to the reaction tank at a constant flow rate.

In the particle growth step, an aqueous solution containing a metalcomponent, such as an aqueous solution containing nickel and the like,may be added to the pH value-adjusted mixed aqueous solution asdescribed above. In this step, the pH value of the mixed aqueoussolution to be obtained is preferably controlled to be to be within thesame range as that for the pH value-adjusted mixed aqueous solution,i.e., greater than or equal to 6.0 and less than or equal to 9.0, morepreferably greater than or equal to 6.4 and less than or equal to 8.0,and still more preferably greater than or equal to 7.1 and less than orequal to 8.0. The pH value of the mixed aqueous solution is adjusted inthe above manner for the same reason as that for adjusting the pH valuebefore starting the particle growth step.

By controlling the pH value of the mixed aqueous solution to be withinthe above range in the particle growth step, a precursor with a smallamount of residual impurities may be obtained.

Note that because the pH value of the mixed aqueous solution fluctuatesslightly during the particle growth step, the maximum value of the pHvalue of the mixed aqueous solution during the particle growth step maybe regarded as the pH value of the mixed aqueous solution during theparticle growth step, and such pH value of the mixed aqueous solution ispreferably controlled to be within the above range.

In particular, the fluctuation range of the pH value of the mixedaqueous solution is preferably controlled to be within 0.2 above orbelow a center value (set pH value) during the particle growth step.When the fluctuation range of the pH value of the mixed aqueous solutionis exceeds the above range, the growth of particles contained in theprecursor may not be constant, and uniform particles with a narrowparticle size distribution may not be obtained.

When supplying the aqueous solutions containing metal components or themetal component-containing mixed aqueous solution as described above, apH adjustment aqueous solution is preferably supplied along with theaqueous solutions containing metal components or the metalcomponent-containing mixed aqueous solution so that the pH of the mixedaqueous solution can be maintained within a predetermined range. The pHadjustment aqueous solution used in the particle growth step may be thesame as the pH adjustment aqueous solution used in the nucleation step.The pH adjustment aqueous solution used is not particularly limited, butfor example, an aqueous solution containing an alkaline substance and/oran ammonium ion supplier may be used. Note that the alkaline substanceand the ammonium ion supplier are not particularly limited, but the samesubstances as those that may be used in the initial aqueous solution maybe used, for example. The method of supplying the pH adjustment aqueoussolution into the reaction tank is not particularly limited, but forexample, while sufficiently stirring the obtained mixed aqueoussolution, the pH adjustment aqueous solution may be added using a pumpcapable of flow rate control, such as a metering pump, so that the pHvalue can be maintained within a predetermined range.

In the particle growth step, the ammonium ion concentration in the mixedaqueous solution is preferably controlled to be greater than or equal to0 g/L and less than or equal to 20 g/L, and is more preferablymaintained at a constant value.

By controlling the ammonium ion concentration to be less than or equalto 20 g/L, nuclei of precursor particles may be homogeneously grown.Also, by maintaining the ammonium ion concentration at a constant valuein the grain growth step, the solubility of metal ions can be stabilizedand uniform growth of the precursor particles can be promoted.

Note that the lower limit of the ammonium ion concentration is notparticularly limited and can be adjusted to a suitable value asnecessary. Accordingly, the ammonium ion concentration in the mixedaqueous solution is preferably adjusted to be greater than or equal to 0g/L and less than or equal to 20 g/L by adjusting the amount of ammoniumion supplier supplied to the initial aqueous solution and/or the pHadjustment aqueous solution, for example.

In the particle growth step, an aqueous solution containing a metalcomponent such as an aqueous solution containing nickel may be added andmixed into the mixed aqueous solution under the presence of carbonateions. In this step, the method of supplying carbonate ions is notparticularly limited, but for example, carbon dioxide may be supplied tothe mixed aqueous solution by supplying carbon dioxide gas together withan oxygen-containing gas into the reaction tank as described below. Thecarbonate ions may also be supplied using a carbonate salt whenpreparing the initial aqueous solution or the pH adjustment aqueoussolution, for example.

In the particle growth step, an aqueous solution containing a metalcomponent such as an aqueous solution containing nickel as a metalcomponent may be supplied at a constant flow rate, for example, while anoxygen-containing gas is blown into the reaction tank to control theatmosphere in the reaction tank to be an oxygen-containing atmosphere.In this way, dissolved oxygen contained in the mixed aqueous solutionand oxygen contained in the oxygen-containing gas supplied to thereaction tank may promote a reaction so that amorphous fine particleswhich are not single crystals of carbonate may be further aggregated toform large secondary particles. Also, by blowing an oxygen-containinggas into the reaction tank, a hydrogen-containing functional group maybe more easily mixed with the precursor as compared with the case ofperforming the particle growth step in an inert gas atmosphere, and H/Merepresenting the ratio of the amount of hydrogen H to the amount ofmetal components Me contained in the resulting precursor may becontrolled to be greater than or equal to 1.60.

In the case of supplying the oxygen-containing gas into the reactiontank in the particle growth step, the amount of the oxygen-containinggas to be supplied may be determined by measuring the concentration ofdissolved oxygen in the mixed aqueous solution. Because dissolved oxygenin the mixed aqueous solution is consumed during the particle growthstep, the amount of dissolved oxygen/oxygen supplied may be deemedsufficient for promoting a reaction if the amount of dissolved oxygen inthe mixed aqueous solution is more than half the saturation amount.

Note that air may be used as the oxygen-containing gas, for example.

The particle diameter of the secondary particles contained in theprecursor may be controlled by controlling the reaction time in theparticle growth step.

That is, in the particle growth step, if a reaction is continued untilparticles are grown to a desired particle size, a precursor havingsecondary particles of a desired particle size can be obtained.

After the precursor is obtained in the grain growth step, the obtainedprecursor may be further subjected to a coating step of coating theadditional element on the surfaces of the precursor particles asdescribed above. That is, the precursor manufacturing method accordingto the present embodiment may further include a coating step of coatingthe additional element over the particles (secondary particles) of theprecursor obtained in the particle growth step.

The coating step may be implemented by one of the following processsteps, for example.

For example, the coating step may be a process step that involves addingthe additional element-containing aqueous solution to a slurrycontaining suspended precursor particles, and precipitating theadditional element on the surfaces of the precursor particles by acrystallization reaction.

In preparing the slurry containing the suspended precursor particles,the precursor particles are preferably turned into a slurry using theadditional element-containing aqueous solution. Also, when adding theadditional element-containing aqueous solution to the slurry containingthe suspended precursor particles, the pH value of a mixed aqueoussolution obtained by mixing together the slurry and the additionalelement-containing aqueous solution is preferably controlled to begreater than or equal to 6.0 and less than or equal to 9.0. Bycontrolling the pH value of the mixed aqueous solution of the slurry andthe additional element-containing aqueous solution to be within theabove range, the surfaces of the precursor particles can be uniformlycoated with the additional element.

Also, the coating step may be a process step that involves spraying theadditional element-containing aqueous solution or a slurry onto theprecursor particles and drying the precursor particles, for example.

The coating step may also be a process step that involves spray drying aslurry containing suspensions of the precursor particles and a compoundcontaining the additional element.

The coating step may also be a process step that involves mixingtogether the precursor particles and a compound containing theadditional element by a solid phase method, for example.

Note that the additional element-containing aqueous solution used in thecoating step may be the same as the additional element-containingaqueous solution used in the nucleation step. Also, in the coating step,an alkoxide solution containing the additional element may be usedinstead of the additional element-containing aqueous solution, forexample.

In the case where the additional element-containing aqueous solution isadded to the initial aqueous solution and/or the mixed aqueous solutionin the nucleation step and/or the particle growth step as describedabove, and the coating step is performed to coat the surfaces of theprecursor particles with the additional element, the amount ofadditional element ions to be added to the initial aqueous solutionand/or the mixed aqueous solution in the nucleation step and/or theparticle growth step is preferably reduced by the amount of additionalelement to be coated on the precursor particles. By reducing the amountof the additional element-containing aqueous solution to be added to themixed aqueous solution by the amount of the additional element to becoated on the precursor particles, the atom number ratio of theadditional element contained in the precursor with respect to the othermetal components contained in the precursor can be controlled to adesired value.

Note that the coating step of coating the surfaces of the precursorparticles with the additional element as described above may beperformed on the precursor particles that have been heated aftercompletion of the particle growth step.

The precursor manufacturing method according to the present embodimentis preferably implemented by an apparatus that does not collect theprecursor corresponding to the reaction product until reactions from thenucleation step to the particle growth step are completed. An example ofsuch an apparatus includes a commonly used batch reaction tank equippedwith a stirrer and the like. By using such an apparatus, problemsassociated with growing particles being collected along with overflowfluid (problems encountered in conventional continuous crystallizationapparatuses that collect products using overflow fluid) may be avoided,and in this way, particles having a narrow particle size distributionand uniform particle size can be obtained.

Also, an apparatus that is capable of controlling the atmosphere, suchas a sealed apparatus, is preferably used so that the atmosphere of thereaction tank can be controlled.

By using an apparatus that is capable of controlling the atmosphere ofthe reaction tank, particles contained in the precursor may becontrolled to have the configurations as described above and asubstantially uniform coprecipitation reaction may be promoted. In thisway, particles having a desirable particle size distribution, i.e.,particles having a narrow particle size distribution, can be obtained.

In the particle growth step, the pH value of the mixed aqueous solutionobtained in the nucleation step may be adjusted to be within apredetermined range, and an aqueous solution containing a metalcomponent such as an aqueous solution containing nickel may be furtheradded to the mixed aqueous solution to obtain uniform precursorparticles.

By performing the above particle growth step, a precursorparticle-containing aqueous solution corresponding to a slurrycontaining precursor particles may be obtained. After the particlegrowth step is completed, a washing step and a drying step may beperformed.

(3) Washing Step

In the washing step, the slurry containing the precursor particlesobtained in the particle growth step described above can be washed.

In the washing step, a slurry containing precursor particles isfiltered, washed with water, and filtered again.

The filtration may be performed by a conventional technique using acentrifuge or a suction filtering machine, for example.

Also, the washing with water may be performed by a conventional methodthat can remove excess raw materials and the like contained in theprecursor particles.

The water used in the washing step is preferably water containing aminimum amount of impurities in order to prevent impurity contamination,and more preferably, purified water is used.

(4) Drying Step

In the drying step, the precursor particles washed in the washing stepcan be dried.

For example, in the drying step, the precursor particles can be dried ata drying temperature that is adjusted to be greater than or equal to 80°C. and less than or equal to 230° C.

After the drying step, a precursor can be obtained.

In the precursor manufacturing method according to the presentembodiment, a precursor that is capable forming a positive-electrodeactive material for a nonaqueous electrolyte secondary batterycontaining porous particles can be obtained.

Also, in the precursor manufacturing method according to the presentembodiment, the time during which nucleation reaction mainly occurs(nucleation step) and the time during which particle growth reactionmainly occurs (particle growth step) are clearly separated such thatprecursor particles (secondary particles) having a narrow particle sizedistribution may be obtained even if both steps are carried out in thesame reaction tank.

Also, in the precursor manufacturing method according to the presentembodiment, the crystal size of the precursor particles obtained duringthe crystallization reaction can be controlled.

Thus, in the precursor manufacturing method according to the presentembodiment, a precursor with primary particles having small particlediameters and secondary particles having particle diameter uniformityand high density (tap density) can be obtained.

Also, in the precursor manufacturing method according to the presentembodiment, the nucleation step and the particle growth step can beseparately performed in one reaction tank by simply adjusting the pHvalue of the reaction solution. As such, the precursor manufacturingmethod according to the present embodiment may have substantialindustrial value in that it can be easily implemented and is suitablefor large-scale production.

[Positive-Electrode Active Material for Nonaqueous Electrolyte SecondaryBattery]

In the following, an example configuration of a positive-electrodeactive material for a nonaqueous electrolyte secondary battery(hereinafter also simply referred to as “positive-electrode activematerial”) according to an embodiment of the present invention will bedescribed.

The positive-electrode active material according to the presentembodiment corresponds to a positive-electrode active material for anonaqueous electrolyte secondary battery including a lithium metalcomposite oxide.

The lithium metal composite oxide is represented by general formulaLi_(1+α)Ni_(x)Co_(y)Mn_(z)M_(t)O₂ (where 0.25≤α≤0.55, x+y+z+t=1,0.05≤x≤0.3, 0.1≤y≤0.4, 0.55≤z≤0.8, and M denotes at least one additionalelement selected from a group consisting of Mg, Ca, Al, Ti, V, Cr, Zr,Nb, Mo, and W).

The positive-electrode active material according to the presentembodiment contains porous secondary particles that are aggregations ofa plurality of primary particles. The internal porosity of the secondaryparticles is greater than or equal to 10% and less than or equal to 30%,and the ratio of the number of secondary particles (with respect to thetotal number of particles) is greater than or equal to 80%.

The positive-electrode active material according to the presentembodiment may include a lithium metal composite oxide formed by thesolution of two types layered compounds represented by formulas Li₂M1O₃and LiM2O₂, more specifically, a lithium-rich nickel-cobalt-manganesecomposite oxide. The positive-electrode active material according to thepresent embodiment may also consist of the above lithium metal compositeoxide.

In the above formulas, M1 denotes metal elements including at least Mnthat are adjusted to be tetravalent on average, and M2 denotes metalelements including at least Ni, Co, and Mn that are adjusted to betrivalent on average.

It is assumed that the composition ratios of Ni, Co, and Mn in theprecursor as described above determine the composition of M1+M2. Also,because the above lithium metal composite oxide is a lithium-rich metalcomposite oxide, the presence ratios of Li₂M1O₃ and LiM2O₂ are adjustedso that the presence ratio of Li₂M1O₃ is not 0%.

As described above in connection with the precursor, in order to furtherimprove battery characteristics, such as cycle characteristics andoutput characteristics, of the positive-electrode active material forthe nonaqueous electrolyte secondary battery, the lithium metalcomposite oxide may also contain at least one additional elementselected from the group consisting of Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo,and W. Also, for the reasons described above in connection with theprecursor, the amount of additional element contained in the lithiummetal composite oxide is preferably adjusted so that the atom numberratio t of the additional element M in the lithium metal composite oxideis within the range of

As described above, the additional element may be at least one elementselected from the group consisting of Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo,and W. In particular, the additional element preferably includesmolybdenum (Mo). That is, in the above general formulaLi_(1-α)Ni_(x)Co_(y)Mn_(z)M_(t)O₂, the additional element M preferablyincludes Mo. According to studies conducted by the inventors of thepresent invention, when the positive-electrode active material containsmolybdenum as an additional element, the initial discharge capacity of abattery using the positive-electrode active material can be particularlyincreased.

Further, in the lithium metal composite oxide, the content ratio ofmolybdenum in the metal components other than Li of the lithium metaloxide, i.e., the metal components Ni, Co, Mn, and the additional elementM, is adjusted to be greater than or equal to 0.5 at % and less than orequal to 5 at %. By controlling the content ratio of molybdenum in themetal components other than Li of the lithium metal composite oxide tobe greater than or equal to 0.5 at %, the above-described effect ofincreasing the initial discharge capacity can be particularly enhanced.Also, although molybdenum has an effect of promoting sintering during afiring process, by controlling the content of molybdenum in the metalcomponents other than Li of the lithium metal composite oxide to be lessthan or equal to 5 at %, generation of excessively large crystals may beprevented such that an increase in resistance and a decrease indischarge capacity of a battery fabricated using the precursor can bereliably prevented.

Further, studies conducted by the inventors of the present inventionrevealed that by including molybdenum in the additional element, thespecific surface area of the positive-electrode active material preparedusing the precursor can be reduced. This is because by addingmolybdenum, fine pores in the positive-electrode active material may bestructurally changed to larger pores. Further, according to studiesconducted by the inventors of the present invention, by controlling thespecific surface area of the positive-electrode active material to begreater than or equal to 1.5 m²/g and less than or equal to 15.0 m²/g, apositive electrode mixed material paste may be easily manufactured andoutput characteristics may be increased. Thus, molybdenum is preferablyincluded in the additional element also from the perspective ofcontrolling the specific surface area to be within the above range.

The positive-electrode active material according to the presentembodiment includes secondary particles having porous structures withuniform fine pores extending into their cores. By arranging thesecondary particles to have such a porous structure, the reactionsurface area can be increased. Also, an electrolytic solution canpermeate through particle boundaries between primary particles or thefine pores at the outer shell portion into the particle interior toenable lithium insertion/deinsertion even at a reaction interface insidethe particle so that movement of Li ions and electrons may beundisturbed and output characteristic may be enhanced.

In the positive-electrode active material according to the presentembodiment, the porosity of the secondary particles is preferablygreater than or equal to 10% and less than or equal to 30%. Also, theratio of the number of such porous secondary particles having uniformfine pores included in the positive-electrode active material (withrespect to the total number of particles) is preferably greater than orequal to 80%. Note that the porosity of the porous secondary particlesmay be obtained by observing a cross-sectional structure of thepositive-electrode active material using a scanning electron microscope(SEM) and calculating the porosity through image processing, forexample. Also, the number ratio of the porous secondary particles may beobtained by observing cross-sectional structures of a plurality of(e.g., 100) secondary particles of the positive-electrode activematerial using a SEM, for example, and counting the number of secondaryparticles having porous structures with fine pores extending into theircores.

By arranging the positive-electrode active material according to thepresent embodiment to have a porous structure, the specific area of thepositive-electrode active material may be increased. The specificsurface area of the positive-electrode active material according to thepresent embodiment is not particularly limited and may be selectivelydetermined based on the required characteristics of thepositive-electrode active material. For example, the specific surfacearea of the positive-electrode active material is preferably greaterthan or equal to 1.5 m²/g. By arranging the specific surface area of thepositive-electrode active material to be greater than or equal to 1.5m²/g, a positive electrode mixed material paste may be easilymanufactured and output characteristics may be increased.

Also, the upper limit of the specific surface area of thepositive-electrode active material is not particularly limited, but forexample, the specific surface area is preferably arranged to be lessthan or equal to 15.0 m²/g, and more preferably less than or equal to13.0 m²/g.

Note that when an increase in the reaction surface area and an increasein the output characteristics are particularly desired, the specificsurface area of the positive-electrode active material according to thepresent embodiment is preferably arranged to be greater than or equal to5.0 m²/g and less than or equal to 15.0 m²/g. Also, when facilitation ofthe manufacture of a positive-electrode mixed material paste isparticularly desired, the specific surface area of thepositive-electrode active material according to the present embodimentis preferably arranged to be greater than or equal to 1.5 m²/g and lessthan or equal to 8.0 m²/g.

Also, by arranging the positive-electrode active material according tothe present embodiment to have a porous structure, outputcharacteristics of a battery formed using the positive-electrode activematerial may be increased and the tap density of the positive-electrodeactive material may be increased.

The tap density of the positive-electrode active material according tothe present embodiment is not particularly limited but is preferablygreater than or equal to 1.7 g/cc, and more preferably greater than orequal to 1.8 g/cc.

The positive-electrode active material according to the presentembodiment preferably has a high initial discharge capacity that isgreater than or equal to 250 mAh/g when used as a positive-electrode ofa 2032-type coin battery, for example. Also, the discharge capacityunder a high discharge rate condition (2C) is preferably greater than orequal to 195 mAh/g.

Note that the discharge capacity under the above high discharge ratecondition (2C) may be obtained by measuring the discharge capacity underthe 2C discharge rate a plurality of times (e.g., three times) andcalculating an average value of the plural measurements, for example.

[Method for Manufacturing Positive-Electrode Active Material forNonaqueous Electrolyte Secondary Battery]

In the following, an example method for manufacturing apositive-electrode active material for a nonaqueous electrolytesecondary battery (hereinafter also simply referred to as“positive-electrode active material manufacturing method”) according toan embodiment of the present invention will be described.

Although the positive-electrode active material manufacturing methodaccording to the present embodiment is not particularly limited as longas a positive-electrode active material having the above-describedparticle structure can be manufactured, the following method maypreferably be used to reliably manufacture the positive-electrode activematerial.

For example, the positive-electrode active material manufacturing methodaccording to the present embodiment may include the following steps.

A heat treatment step of heat-treating the positive-electrode activematerial precursor for a nonaqueous electrolyte secondary batteryobtained by the above-described method for manufacturing apositive-electrode active material precursor for a nonaqueouselectrolyte secondary battery at a temperature greater than or equal to80° C. and less than or equal to 600° C.

A mixing step of adding and mixing a lithium compound into the particlesobtained by the heat treatment step to form a lithium mixture.

A firing step of firing the lithium mixture in an oxidizing atmosphereat a temperature greater than or equal to 600° C. and less than or equalto 1000° C.

In the following, each of the above steps will be described.

(1) Heat Treatment Step

In the heat treatment step, the above-described precursor may beheat-treated at a temperature greater than or equal to 80° C. and lessthan or equal to 600° C. By performing the heat treatment, moisturecontained in the precursor can be removed, and variations in the ratiosof the number of metal atoms and the number of lithium atoms in thepositive-electrode active material to be ultimately obtained can beprevented.

Note that the moisture removal may be performed to the extent necessaryto prevent variations in the ratios of the number of metal atoms and thenumber of lithium atoms in the positive-electrode active material. Assuch, it may not be necessary to convert all the precursor particlesinto nickel-cobalt-manganese composite oxide. However, in order tofurther reduce the variations in the atom number ratios, the heattreatment temperature is preferably arranged to be greater than or equalto 500° C., and all the precursor particles are preferably convertedinto composite oxide particles.

Note that the heat treatment temperature is arranged to be greater thanor equal to 80° C. in the heat treatment step because excessive moisturein the precursor particles may not be adequately removed and variationsin the atom number ratios may not be adequately prevented if the heattreatment temperature is lower than 80° C.

On the other hand, the heat treatment temperature is arranged to be lessthan or equal to 600° C. in the heat treatment step because particlesmay be sintered due to burning and composite oxide particles withuniform particle diameters may not be obtained if the heat treatmenttemperature is above 600° C.

By determining the metal components contained in the precursor particlescorresponding to the heat treatment conditions through analysis inadvance and determining the ratio of the metal compounds to the lithiumcompound, the above-described variations may be prevented.

The heat treatment atmosphere is not particularly limited as long as theheat treatment is performed in a non-reducing atmosphere, but forexample, the heat treatment step can be conveniently performed in anairflow.

Although the heat treatment time is not particularly limited, the heattreatment is preferably performed for at least 1 hour, and morepreferably for at least 2 hours and no more than 15 hours. Note that ifthe heat treatment is performed for less than 1 hour, excessive moisturein the precursor particles may not be adequately removed.

The equipment used for the heat treatment is not particularly limited aslong as the precursor particles can be heated in a non-reducingatmosphere, preferably in an airflow. For example, an electric furnacethat does not generate gas may preferably be used.

(2) Mixing Step

In the mixing step, a lithium compound is added to and mixed with theheat-treated particles obtained by heating the precursor particles inthe heat treatment step to form a lithium mixture.

Note that the heat-treated particles obtained by heating the precursorparticles in the heat treatment step include nickel-cobalt-manganesecarbonate composite particles and/or nickel-cobalt-manganese compositeoxide particles.

The heat-treated particles and the lithium compound are preferably mixedtogether such that, provided Li/Me represents the ratio of the number oflithium atoms (Li) to the number of atoms constituting the metalcomponents other than lithium in the lithium mixture, i.e., the totalnumber of atoms of nickel, cobalt, manganese, and the additional elementM (Me) in the lithium mixture, Li/Me is greater than or equal to 1.1 andless than or equal to 1.8. More preferably, the heat-treated particlesand the lithium compound are mixed together such that the ratio Li/Me isgreater than or equal to 1.3 and less than or equal to 1.5.

That is, because no change occurs in the ratio Li/Me before and afterthe firing step, the ratio Li/Me in the lithium mixture obtained in themixing step becomes the ratio Li/Me in the positive-electrode activematerial. As such, the ratio Li/Me in the lithium mixture is adjusted tobe substantially the same as the ratio Li/Me in the positive-electrodeactive material to be manufactured.

The lithium compound to be used for forming the lithium mixture is notparticularly limited, but for example, at least one compound selectedfrom a group consisting of lithium hydroxide, lithium nitrate, andlithium carbonate may be used in view of the accessibility the abovecompounds.

In particular, in consideration of ease of handling and qualitystability, at least one compound selected from a group consisting oflithium hydroxide and lithium carbonate is preferably used as thelithium compound for forming the lithium mixture.

Note that a general mixer can be used to mix the lithium compound in themixing step. For example, a shaker mixer, a Lödige mixer, a Julia mixer,a V blender, or the like may be used.

(3) Firing Step

The firing step is a step of firing the lithium mixture obtained in themixing step to obtain a positive-electrode active material. When thelithium mixture is fired in the firing step, lithium in the lithiumcompound diffuses into the heat treated particles so that alithium-nickel-cobalt-manganese composite oxide is formed.

The firing temperature of the lithium mixture is not particularlylimited, but for example, the firing temperature is preferably greaterthan or equal to 600° C. and less than or equal to 1000° C.

By controlling the firing temperature to be greater than or equal to600° C., diffusion of lithium into the heat-treated particles may besufficiently promoted, excessive lithium and unreacted particles may beprevented from remaining in the positive-electrode active material, andadequate battery characteristics may be obtained when the positiveelectrode active material is used in a battery.

However, when the firing temperature exceeds 1000° C., rampant sinteringof the composite oxide particles and abnormal particle growth may occur,and the fired particles may become coarse such that minute pores may notbe formed inside the particles. As a result, the specific surface areaof the positive-electrode active material may be reduced, and thepositive-electrode resistance may increase and the battery capacity maydecrease in a battery using such positive-electrode active material.

Because the firing temperature of the lithium mixture also affects thespecific surface area of the positive-electrode active material to beobtained, the firing temperature can be selectively adjusted to asuitable temperature within the above-described temperature range inview of the specific surface area required for the positive-electrodeactive material. For example, when a relatively small specific surfacearea of the positive electrode active material is particularly desired,the firing temperature is preferably set to a higher temperature greaterthan or equal to 900° C. and less than or equal to 950° C. According tostudies conducted by the inventors of the present invention, bycontrolling the firing temperature to be within the above-describedtemperature range, the specific surface area of the positive-electrodeactive material may be greater than or equal to 1.5 m²/g and less thanor equal to 8.0 m²/g, and a positive-electrode mixed material paste maybe easily manufactured. Also, when a nonaqueous electrolyte secondarybattery is manufactured using such positive-electrode active material, adesirably high battery capacity can be obtained.

Note that from the perspective of promoting uniform reaction between theheat-treated particles and the lithium compound, the temperature ispreferably raised to the above firing temperature at a temperatureincrease rate that is greater than or equal to 3° C./min and less thanor equal to 10° C./min.

Further, by maintaining the temperature close to the melting point ofthe lithium compound for about 1 hour to 5 hours, a more uniformreaction can be promoted. In the case where the temperature ismaintained close to the melting point of the lithium compound, thetemperature can thereafter be raised to a predetermined firingtemperature.

In the firing step, the firing temperature is preferably maintained forat least 1 hour, and more preferably for a time period greater than orequal to 2 hours and less than or equal to 24 hours.

By maintaining the firing temperature for at least 2 hours, formation ofa lithium-nickel-cobalt-manganese composite oxide can be adequatelypromoted.

After maintaining the firing temperature for the above time period,although not particularly limited, in the case where the lithium mixtureis loaded in a sagger in the firing step, the temperature is preferablydecreased to be less than or equal to 200° C. at a decrease rate that isgreater than or equal to 2° C./min and less than or equal to 10° C./minin order to prevent deterioration of the sagger.

The atmosphere during firing is preferably an oxidizing atmosphere, morepreferably an atmosphere having an oxygen concentration that is greaterthan or equal to 18 vol % and less than or equal to 100 vol %, and morepreferably a mixed-gas atmosphere including oxygen at the above oxygenconcentration and an inert gas. That is, firing is preferably carriedout in atmospheric air or in an oxygen-containing gas.

The oxygen concentration in the atmosphere during firing is preferablyadjusted to be greater than or equal to 18 vol % as described above sothat the crystallinity of the lithium-nickel-cobalt-manganese compositeoxide may be adequately increased.

In particular, firing is preferably carried out in an oxygen airflow inconsideration of battery characteristics.

Note that the furnace used in the firing step is not particularlylimited as long as it is capable of heating the lithium mixture inatmospheric air or in an oxygen-containing gas. However, from theperspective of maintaining a uniform atmosphere within the furnace, anelectric furnace that does not generate gas is preferably used. Also,note that either a batch type furnace or a continuous type furnace maybe used.

Also, in the case where lithium hydroxide or lithium carbonate is usedas the lithium compound, calcination is preferably performed aftercompleting the mixing step, before performing the firing step. Thecalcination temperature is lower than the firing temperature, and ispreferably greater than or equal to 350° C. and less than or equal to800° C., and more preferably greater than or equal to 450° C. and lessthan or equal to 780° C.

The calcination is preferably performed for about 1 hour to 10 hours,and more preferably for about 3 hours to 6 hours.

Note that calcination is preferably performed by maintaining thetemperature at the above calcination temperature. In particular,calcination is preferably performed at the reaction temperature for thereaction between lithium hydroxide or lithium carbonate and theheat-treated particles.

By performing calcination in the above-described manner, lithium may beadequately diffused into the heat-treated particles, and a uniformlithium-nickel-cobalt-manganese composite oxide may be obtained.

Note that aggregation or a mild sintering of thelithium-nickel-cobalt-manganese composite oxide particles obtained bythe firing step may occur in some cases.

In such case, the lithium-nickel-cobalt-manganese composite oxideparticles may be disintegrated. In this way, the positive-electrodeactive material including the lithium-nickel-cobalt-manganese compositeoxide according to the present embodiment can be obtained.

Note that disintegration refers to a process of dissociating andseparating secondary particles that have been aggregated while avoidingdestruction of the secondary particles themselves by introducingmechanical energy to the aggregated secondary particles that have beenformed by the necking (sintering) of the secondary particles in thefiring step, for example.

[Nonaqueous Electrolyte Secondary Battery]

In the following, an example configuration of a nonaqueous electrolytesecondary battery according to an embodiment of the present inventionwill be described. The nonaqueous electrolyte secondary batteryaccording to the present embodiment may have a positive electrode thatuses the above-described positive-electrode active material.

First, the structure of the nonaqueous electrolyte secondary batteryaccording to the present embodiment will be described below.

The nonaqueous electrolyte secondary battery according to the presentembodiment (hereinafter also simply referred to as “secondary battery”)may have a structure that is substantially identical to that of ageneral nonaqueous electrolyte secondary battery except that theabove-described positive-electrode active material is used as thepositive electrode material for its positive electrode.

For example, the secondary battery according to the present embodimentmay include a case having a positive electrode, a negative electrode, anonaqueous electrolyte, and a separator accommodated therein.

More specifically, the secondary battery according to the presentembodiment may include an electrode body that is configured by stackinga positive electrode and a negative electrode via a separator. Theelectrode body may be impregnated with the nonaqueous electrolyte. Apositive electrode current collector of the positive electrode may beconnected to a positive electrode terminal communicating with theoutside using a current collection lead, for example, and a negativeelectrode current collector of the negative electrode may be connectedto a negative electrode terminal communicating with the outside using acurrent collection lead, for example. The electrode body having such astructure may be sealed within the case.

Note that the structure of the secondary battery according to thepresent embodiment is not limited to the above example. Also, thesecondary battery can be in various formats, such as the cylinder formator the laminated format, for example.

(Positive Electrode)

In the following, the positive electrode of the secondary batteryaccording to the present embodiment will be described. The positiveelectrode is a sheet member and is formed by coating and drying apositive electrode mixed material paste containing the above-describedpositive electrode active material on the surface of a current collectormade of aluminum foil, for example.

Note that the positive electrode is appropriately treated according tothe specific battery in which the positive electrode is used. Forexample, a cutting process may be performed to form the positiveelectrode into an appropriate size for a target battery, and a pressurecompression process such as a roll press may be performed to increasethe electrode density.

The positive electrode mixed material paste may be formed by adding asolvent to a positive electrode mixed material and kneading the positiveelectrode mixed material. The positive electrode mixed material may beformed by mixing the above-described positive electrode active materialthat is in powder form with a conductive material and a binder.

The conductive material is added to give appropriate conductivity to theelectrode. The conductive material is not particularly limited, but forexample, graphite (natural graphite, artificial graphite, expandedgraphite, etc.) or carbon black material, such as acetylene black orketjen black, may be used.

The binder is for binding together the positive electrode activematerial particles. The binder used in the positive electrode mixedmaterial is not particularly limited, but for example, polyvinylidenefluoride (PVDF), polytetrafluoroethylene (PTFE), fluororubber, ethylenepropylene diene rubber, styrene butadiene, cellulose resin, polyacrylicacid, and the like may be used.

Note that activated carbon or the like may be added to the positiveelectrode mixed material, for example. By adding activated carbon or thelike, the electric double layer capacity of the positive electrode maybe increased.

The solvent dissolves the binder and causes the positive-electrodeactive material, the conductive material, the activated carbon, and thelike to disperse in the binder. The solvent is not particularly limited,but for example, an organic solvent such as N-methyl-2-pyrrolidone maybe used.

Note that the mixing ratio of each substance in the positive electrodemixed material paste is not particularly limited. For example, assumingthe solid content of the positive electrode mixed material (i.e.,components of the positive electrode mixed material paste other than thesolvent) is 100 parts by mass, as in a positive electrode of a generalnonaqueous electrolyte secondary battery, the content of thepositive-electrode active material may be adjusted to be greater than orequal to 60 parts by mass and less than or equal to 95 parts by mass,the content of the conductive material may be adjusted to be greaterthan or equal to 1 part by mass and less than or equal to 20 parts bymass, and the content of the binder may be adjusted to be greater thanor equal to 1 part by mass and less than or equal to 20 parts by mass.

(Negative Electrode)

The negative electrode is a sheet member formed by applying a negativeelectrode mixed material paste on the surface of a metal foil currentcollector made of copper foil, for example, and drying the sheet member.Although the components of the negative electrode mixed material paste,the mix ratio thereof, and the material of the current collector may bedifferent from the positive electrode, the negative electrode may beformed in substantially the same manner as the positive electrode. Also,as with the positive electrode, the negative electrode may be subjectedto various treatments according to the target battery.

The negative electrode mixed material paste is a paste prepared byadding a suitable solvent to a negative electrode mixed materialobtained by mixing together a negative-electrode active material and abinder.

The negative-electrode active material may be a material containinglithium, such as metallic lithium or a lithium alloy, or an insertionmaterial capable of sustaining insertion and deinsertion of lithiumions, for example.

The insertion material is not particularly limited, but for example, anorganic compound fired body, such as natural graphite, artificialgraphite, or a phenolic resin, or a powder of a carbon substance such ascoke (petroleum coke) may be used. When such a material is used as thenegative-electrode active material, as with the positive electrode, afluorine-containing resin such as PVDF may be used as the binder, and anorganic solvent such as N-methyl-2-pyrrolidone may be used as thesolvent for dispersing the negative electrode active material in thebinder.

(Separator)

The separator is interposed between the positive electrode and thenegative electrode and has a function of separating the positiveelectrode and the negative electrode and holding the electrolyte. Such aseparator may be a thin film of polyethylene or polypropylene having alarge number of fine pores, for example. However, the separator is notparticularly limited as long as it has the above function.

(Nonaqueous Electrolyte)

The nonaqueous electrolyte is obtained by dissolving a lithium salt as asupporting salt in an organic solvent.

Examples of the organic solvent include cyclic carbonates, such asethylene carbonate, propylene carbonate, butylene carbonate, andtrifluoropropylene carbonate; chain carbonates, such as diethylcarbonate, dimethyl carbonate, ethylmethyl carbonate, and dipropylcarbonate; ether compounds, such as tetrahydrofuran,2-methyltetrahydrofuran, and dimethoxyethane; a sulfur compound, such asethylmethylsulfone and butane sultone; phosphorus compounds, such astriethyl phosphate and trioctyl phosphate. These substances may be usedalone or in combination as the organic solvent.

Examples of the supporting salt include LiPF₆, LiBF₄, LiClO₄, LiAsF₆,LiN(CF₃SO₂)₂, and complex salts thereof.

The nonaqueous electrolyte may also contain a radical scavenger, asurfactant, a flame retardant, and the like in order to improve batterycharacteristics.

Characteristics of Nonaqueous Electrolyte Secondary Battery According toPresent Embodiment

The nonaqueous electrolyte secondary battery according to the presentembodiment may have the above-described structure, for example. Becausethe nonaqueous electrolyte secondary battery according to the presentembodiment has a positive electrode that is formed using theabove-described positive-electrode active material, high initialdischarge capacity and low positive electrode resistance may be obtainedto thereby achieve high capacity and high output.

Application of Secondary Battery According to Present Embodiment

In view of the above-described characteristics, the secondary batteryaccording to the present embodiment may be suitably used as a powersource of a small portable electronic device (notebook personalcomputer, mobile phone terminal, etc.) that requires high capacity.

Also, the secondary battery according to the present embodiment may besuitably used as a motor driving power source that requires high output.Note that when the size of a battery is increased, it becomes difficultto ensure safety such that an expensive protection circuit becomesindispensable. However, the secondary battery according to the presentembodiment has excellent safety, and as a result, safety can be easilyensured, a protection circuit can be simplified, and manufacturing costscan be reduced. Because the secondary battery according to the presentembodiment can be reduced in size and have increased output power, itcan be suitably used as a power source for transportation equipmenthaving restricted mounting space, for example.

EXAMPLES

In the following, the present invention will be described morespecifically with reference to examples. However, the present inventionis not limited to the following examples.

Sample preparation conditions and sample evaluation results of eachexample and comparative example are described below.

Example 1

1. Precursor Manufacture and Evaluation

First, a precursor was prepared by the following procedure.

Note that in all the examples and comparative examples described below,unless otherwise specified, reagent special grade samples manufacturedby Wako Pure

Chemical Industries, Ltd. were used to manufacture precursors,positive-electrode active materials and secondary batteries.

(Nucleation Step)

(1) Initial Aqueous Solution Preparation

First, a reaction tank (5 L) was filled with about 1.2 L of water, andwhile stirring the water, the temperature inside the reaction tank (5 L)was set to 40° C. so that the temperatures of mixed aqueous solutions ina nucleation step, a nuclei disintegration step, and a particle growthstep as described below would be controlled to 40° C. Note that thetemperatures of the initial aqueous solution and the mixed aqueoussolutions were controlled by adjusting the temperature of reaction tankheating water arranged around the reaction tank.

Then, an appropriate amount of 25 mass % ammonia water was added to thewater in the reaction tank, and the ammonium ion concentration in theinitial aqueous solution was adjusted to 5 g/L.

Further, 64% sulfuric acid was added to the initial aqueous solution toadjust the pH to 6.4.

Then, air gas as an oxygen-containing gas was supplied into the reactiontank from an air compressor at 4 L/min, and the interior of the reactiontank was purged to obtain an oxygen-containing atmosphere. The supply ofthe air gas was continued until the particle growth step was completedso that an air atmosphere, i.e., oxygen-containing atmosphere, could bemaintained within the reaction tank.

(2) Metal Component-Containing Mixed Aqueous Solution Preparation

Next, nickel sulfate, cobalt sulfate, and manganese sulfate weredissolved in water to prepare a metal component-containing mixed aqueoussolution with a metal ion concentration of 2.0 mol/L. In this metalcomponent-containing mixed aqueous solution, the molar ratio of therespective metal elements was adjusted so thatNi:Co:Mn=0.165:0.165:0.67.

(3) pH Adjustment Aqueous Solution Preparation

Sodium carbonate and ammonium carbonate were dissolved in water toprepare a pH adjustment aqueous solution with a carbonate ionconcentration of 2.2 mol/L. Note that the sodium carbonate and theammonium carbonate were added to the pH adjustment aqueous solution suchthat the molar ratio of the sodium carbonate to the ammonium carbonatewould be 9:2.

(4) Adding and Mixing Metal Component-Containing Mixed Aqueous Solutionto Initial Aqueous Solution

The metal component-containing mixed aqueous solution was added to theinitial aqueous solution in the reaction tank at 10.3 ml/min to preparea mixed aqueous solution.

Note that when adding the metal component-containing mixed aqueoussolution, the pH adjustment aqueous solution was also added at the sametime, and while controlling the pH value of the mixed aqueous solutionin the reaction tank to not exceed 6.4 (nucleation pH value), thenucleation step was carried out by promoting crystallization for fourminutes. Also, note that during the nucleation step, the fluctuationrange of the pH value of the mixed aqueous solution was maintainedwithin 0.2 above or below a center value (set pH value) of 6.2.

(5) Disintegration Step

Thereafter, stirring was continued for 5 minutes to disintegrate thenuclei.

(Particle Growth Step)

In the particle growth step, the same metal component-containing mixedaqueous solution and the pH adjustment aqueous solution used in thenucleation step were used. The procedure of the particle growth stepwill be described below.

(1) pH Adjustment of Mixed Aqueous Solution

In the particle growth step, first, the pH adjustment aqueous solutionwas added to the mixed aqueous solution obtained in the nucleation stepto adjust the pH value to 7.4 (liquid temperature of 40° C. as standardtemperature).

(2) Adding and Mixing Metal Component-Containing Mixed Aqueous Solutioninto Mixed Aqueous Solution

The metal component-containing mixed aqueous solution was added to thepH-adjusted mixed aqueous solution at a rate of 10.3 ml/min.

At this time, the amount of the metal component-containing mixed aqueoussolution and the amount of the pH adjustment aqueous solution added tothe mixed aqueous solution were controlled so that the pH value of themixed aqueous solution does not exceed 7.4 at a reaction temperature of40° C. as the standard temperature.

After maintaining the above processing condition for 100 minutes,stirring was stopped and crystallization was terminated.

Then, the product obtained in the particle growth step was washed withwater, filtered, and dried to obtain precursor particles (washing anddrying step).

Note that in the particle growth step, the pH value of the mixed aqueoussolution was controlled by adjusting the supply flow rate of the pHadjustment aqueous solution using a pH controller, and the fluctuationrange of the pH value of the mixed aqueous solution was controlled to beno more than 0.2 above or below a center value (set pH value) of 7.2.

Also, in the nucleation step and the particle growth step, the ammoniumion concentration in the mixed aqueous solution was maintained at 5 g/L.

(Precursor Evaluation)

After dissolving the obtained precursor in an inorganic acid andsubjecting the resulting sample to chemical analysis by ICP emissionspectroscopy, it was confirmed that the sample was a carbonate with thecomposition Ni:Co:Mn=14.9 at %:16.7 at %:68.4 at %. Further, bymeasuring the elemental amount of hydrogen (H) in the sample using anelement analyzer (FlashEA 1112 manufactured by Thermo Fisher Scientific)to calculate the mass ratio of hydrogen (H) to metal (Ni+Co+Mn), it wasconfirmed that the mass ratio was 1.69 indicating that a relativelylarge amount of hydrogen is contained in the sample. Further, it wasconfirmed that the sample includes a hydrogen-containing functionalgroup.

Further, the average particle diameter D₅₀ of the precursor particleswas measured using a laser diffraction/scattering type particle sizedistribution measuring apparatus (Microtrack HRA manufactured by NikkisoCo., Ltd.), and as a result, it was confirmed that the average particlediameter of the precursor particles was 7.4 μm.

Also, by observing the obtained precursor particles using SEM (ScanningElectron Microscope S-4700 manufactured by Hitachi High-TechnologiesCorporation) (magnification: 3000×), it was confirmed that the obtainedprecursor particles were substantially spherical and were uniform inparticle size. Note that in Table 2 shown below, the “precursor particlesphericality” is indicated as “∘” for precursors that were observed tohave particles in such state.

FIG. 2 shows a SEM image of the precursor particles.

2. Positive-Electrode Active Material Manufacture and Evaluation

Next, the obtained precursor was used to manufacture apositive-electrode active material, which was then evaluated.

(Positive-Electrode Active Material Manufacture)

The precursor was heat-treated at 500° C. for 2 hours in an airflow(oxygen: 21% by volume) and converted into composite oxide particles asheat-treated particles, which were then collected.

Next, the heat-treated particles and a lithium compound were mixedtogether to obtain a lithium mixture.

Specifically, lithium carbonate was weighed so that the ratio Li/Me ofthe lithium mixture to be obtained would be 1.5, and the lithiumcarbonate was mixed with the heat-treated particles to prepare thelithium mixture.

The mixing was carried out using a shaker mixer device (TURBULA Type T2Cmanufactured by Willy A. Bachofen (WAB)).

The obtained lithium mixture was calcined at 500° C. for 5 hours in theatmosphere (oxygen: 21% by volume), fired at 800° C. for 2 hours,cooled, and then disintegrated to obtain a positive-electrode activematerial.

Note that the composition of the obtained positive-electrode activematerial can be expressed as Li_(1.5)N_(0.149)Co_(0.167)Mn_(0.684)O₂.

(Positive-Electrode Active Material Evaluation)

The particle size distribution of the obtained positive-electrode activematerial was measured using the same method as that used for measuringthe precursor particles as described above, and as a result, it wasconfirmed that the average particle diameter of the obtainedpositive-electrode active material was 7.0 μm.

Also, cross-sectional SEM observation of the positive-electrode activematerial was performed.

In the cross-sectional SEM observation of the positive-electrode activematerial, secondary particles constituting a plurality ofpositive-electrode active material particles were embedded in resin, theresulting sample was polished using a cross-section polisher to enableobservation of cross sections of the particles, and the sample was thenobserved by SEM.

FIGS. 3A and 3B show cross-sectional SEM images of thepositive-electrode active material. FIG. 3B is a partial enlarged viewof a particle encircled by a dotted line in the SEM image of FIG. 3A.

As can be appreciated from FIGS. 3A and 3B, the particles of theobtained positive-electrode active material were substantiallyspherical. Note that in such case, the “sphericality” of thepositive-electrode active material is indicated as in Table 3. Also, itwas confirmed that the secondary particles had porous structures withuniform fine pores extending into their cores.

Also, by observing 100 or more particles in these sectional SEM images,it was confirmed that the ratio of the number of particles having porousstructures with pores extending into their cores (porous particles) was100%. Also, by measuring the porosity of the porous particles usingimage analysis software, it was confirmed that the porous particles hada porosity of 22%.

Further, measurement of the tap density confirmed that the obtainedpositive-electrode active material had a tap density of 1.8 g/cc.

The tap density was measured after filling the obtainedpositive-electrode active material in a 20-ml graduated cylinder anddensely packing the positive-electrode active material in the cylinderby repeatedly causing the cylinder to free-fall (drop) 500 times from aheight of 2 cm.

Also, by measuring the specific surface area of the positive-electrodeactive material using a flow type gas adsorption specific surface areameasuring apparatus (Multisorb manufactured by Yuasa Ionics Inc.), itwas confirmed that the specific surface area of the positive-electrodeactive material was 12.4 m²/g.

[Secondary Battery Manufacture]

The obtained positive-electrode active material was used to manufacturea 2032-type coin battery, which was then evaluated.

The configuration of the manufactured coin battery will be describedbelow with reference to FIG. 4. FIG. 4 schematically shows across-sectional configuration of a coin battery 10.

As shown in FIG. 4, the coin battery 10 includes a case 11 and anelectrode 12 that is accommodated in the case 11.

The case 11 includes a positive electrode can 111 that is hollow and hasan opening at one end and a negative electrode can 112 that is arrangedin the opening of the positive electrode can 111. The negative electrodecan 112 is arranged in the opening of the positive electrode can 111such that a space for accommodating the electrode 12 is formed betweenthe negative electrode can 112 and the positive electrode can 111.

The electrode 12 includes a positive electrode 121, a separator 122, anda negative electrode 123 that are stacked in above recited order. Theelectrode 12 is accommodated inside the case 11 such that the positiveelectrode 121 comes into contact with the inner surface of the positiveelectrode can 111 and the negative electrode 123 comes into contact withthe inner surface of the negative electrode can 112.

The case 11 also includes a gasket 113 that is fixed between thepositive electrode can 111 and the negative electrode can 112 so thatelectrical insulation may be maintained between the positive electrodecan 111 and the negative electrode can 112. Also, the gasket 113 has afunction of sealing the gap between the positive electrode can 111 andthe negative electrode can 112 and keeping the interior of the case 11airtight and liquid-tight from the outside.

The coin battery 10 was manufactured in the following manner. First,52.5 mg of the obtained positive-electrode active material, 15 mg ofacetylene black and 7.5 mg of polytetrafluoroethylene resin (PTFE) weremixed together with a solvent (N-methyl-2-pyrrolidone), and the mixedmaterial was press-molded into a disk shape with a diameter of 11 mm anda thickness of 100 μm to prepare the positive electrode 121. Theprepared positive electrode 121 was dried in a vacuum dryer at 120° C.for 12 hours. Using the positive electrode 121, the negative electrode123, the separator 122, and an electrolytic solution, the coin battery10 was manufactured in a glove box with an Ar atmosphere that wascontrolled to a dew point of −80° C.

Note that as the negative electrode 123, a negative electrode sheetstamped out into a disk shape with a diameter of 14 mm and formed bycoating graphite powder with an average particle diameter of about 20 μmand polyvinylidene fluoride on a copper foil was used. As the separator122, a porous polyethylene film having a thickness of 25 μm was used. Asthe electrolytic solution, an equal amount mixed solution of ethylenecarbonate (EC) and diethyl carbonate (DEC) using 1 M of LiClO₄ as asupporting electrolyte (manufactured by Toyama Pharmaceutical IndustryCo., Ltd.) was used.

[Battery Evaluation]

The initial discharge capacity for evaluating the performance of theobtained coin battery 10 is defined as follows.

The initial discharge capacity is defined as the capacity of the coinbattery 10 measured after the following procedures have beenimplemented: leaving the coin battery 10 for about 24 hours after itsmanufacture to stabilize the open circuit voltage OCV (open circuitvoltage), charging the coin battery 10 up to a cutoff voltage of 4.65 Vwhile setting the current density with respect to the positive electrodeto 0.05 C (270 mA/g is set to 1C), pausing for 1 hour, and thendischarging the coin battery 10 to a cut-off voltage of 2.35 V.

Upon performing battery evaluation of the coin battery having a positiveelectrode manufactured using the positive-electrode active materialaccording to the present embodiment, it was confirmed that the coinbattery had an initial discharge capacity of 282 mAh/g. Also, in orderto evaluate high discharge rate characteristics, the charge/dischargecapacity was measured at 0.01 C, after which the charge/dischargecapacity was measured at 0.2 C, 0.5 C and 1.0 C three times each, afterwhich the charge/discharge capacity was measured at 2.0 C three times,and the average value of the above measurements was determined as thedischarge capacity at a high discharge rate. The obtained value for theabove coin battery was 216 mAh/g.

Table 1 shows the manufacturing conditions of the present example, Table2 shows the characteristics of the precursor obtained in the presentexample, and Table 3 shows the characteristics of the positive-electrodeactive material obtained in the present example and evaluation resultsof the coin battery manufactured using the obtained positive-electrodeactive material. Note that the above tables show the same informationfor the following Example 2 and Comparative Examples 1 and 2.

Example 2

A precursor, a positive-electrode active material, and a secondarybattery were manufactured and evaluated in the same manner as in Example1, except that the process time of the particle growth step was changedto 196 minutes. The resulting characteristics of the obtained precursor,positive-electrode active material, and secondary battery are shown inTables 1 to 3.

Note that the composition of the obtained positive-electrode activematerial can be expressed as Li_(1.5)Ni_(0.154)Co_(0.167)Mn_(0.679)O₂.

In the present example, it was confirmed that the average particlediameter of the particles contained in the precursor and thepositive-electrode active material could be increased by lengthening theprocess time of the particle growth step. However, it was confirmed thatthe battery characteristics of the secondary battery were the same asthose in Example 1.

Example 3

To add molybdenum as an additional element in the nucleation step andthe particle growth step, an ammonium molybdate solution was added tothe metal component-containing mixed aqueous solution.

Note that the ammonium molybdate solution was added to and mixed withthe metal component-containing mixed aqueous solution such that thecontent ratio of Mo in the transition metal components including Ni, Co,Mn, and Mo of the metal component-containing mixed aqueous solutionwould be 1.5 at %. Note also, that the ratio of the metal components Ni,Co, and Mn in the metal component-containing mixed aqueous solution wasarranged to be the same as that in Example 2.

Aside from using the above-described metal component-containing mixedaqueous solution, a precursor, a positive-electrode active material, anda secondary battery were manufactured and evaluated in the same manneras in Example 2. The resulting characteristics of the obtainedprecursor, positive-electrode active material, and secondary battery areshown in Tables 1 to 3.

The composition of the obtained positive-electrode active material canbe expressed as Li_(1.5)Ni_(0.14)Co_(0.167)Mn_(0.673)Mo_(0.015)O₂.

Example 4

To add molybdenum as an additional element in the nucleation step andthe particle growth step, an ammonium molybdate solution was added tothe metal component-containing mixed aqueous solution.

Note that the ammonium molybdate solution was added to and mixed withthe metal component-containing mixed aqueous solution such that thecontent ratio of Mo in the transition metal components including Ni, Co,Mn, and Mo in the metal component-containing mixed aqueous solutionwould be 3.6 at %. Note also, that the ratio of the metal components Ni,Co, and Mn in the metal component-containing mixed aqueous solution wasarranged to be the same as that in Example 2.

Aside from using the above-described metal component-containing mixedaqueous solution, a precursor, a positive-electrode active material, anda secondary battery were manufactured and evaluated in the same manneras in Example 2. The resulting characteristics of the obtainedprecursor, positive-electrode active material, and secondary battery areshown in Tables 1 to 3.

The composition of the obtained positive-electrode active material canbe expressed as Li_(1.5)Ni_(0.160)Co_(0.175)Mn_(0.629)Mo_(0.06)O₂.

Example 5

A precursor, a positive-electrode active material, and a secondarybattery were manufactured and evaluated in the same manner as in Example2, except that the firing temperature in the firing step was changed to950° C. in manufacturing the positive-electrode active material. Theresulting characteristics of the obtained precursor, positive-electrodeactive material, and secondary battery are shown in Tables 1 to 3.

The composition of the obtained positive-electrode active material canbe expressed as Li_(1.5)Ni_(0.154)Co_(0.167)Mn_(0.679)O₂.

It was confirmed in the present example that by increasing the firingtemperature in the firing step when manufacturing the positive-electrodeactive material, the specific surface area of the positive-electrodeactive material to be obtained can be controlled to be greater than orequal to 1.5 m²/g and less than or equal to 8.0 m²/g that is suitablefor manufacturing a positive electrode mixed material paste. It wasconfirmed that even in such case, the initial discharge capacity and thedischarge capacity under high discharge rate conditions of the secondarybattery can be desirably high.

Example 6

A precursor, a positive-electrode active material, and a secondarybattery were manufactured and evaluated in the same manner as in Example2, except that the firing temperature in the firing step was changed to900° C. when manufacturing the positive-electrode active material. Theresulting characteristics of the obtained precursor, positive-electrodeactive material, and secondary battery are shown in Tables 1 to 3.

The composition of the obtained positive-electrode active material canbe expressed as Li_(1.5)Ni_(0.154)Co_(0.167)Mn_(0.679)O₂.

It was confirmed in the present example that by increasing the firingtemperature in the firing step when manufacturing the positive-electrodeactive material, the specific surface area of the positive-electrodeactive material to be obtained can be controlled to be greater than orequal to 1.5 m²/g and less than or equal to 8.0 m²/g that is suitablefor manufacturing a positive electrode mixed material paste. It wasconfirmed that even in such case, the initial discharge capacity and thedischarge capacity under high discharge rate conditions of the secondarybattery can be desirably high.

Comparative Example 1

A precursor, a positive-electrode active material, and a secondarybattery were manufactured and evaluated in the same manner as in Example1, except that air was not blown into the reaction tank duringmanufacture of the precursor and the process time of the particle growthstep was changed to 110 minutes. The resulting characteristics of theobtained precursor, positive-electrode active material, and secondarybattery are shown in Tables 1 to 3.

As described above, no air was blown into the reaction tank whenmanufacturing the precursor in the present example, and as a result, theatmosphere within the reaction tank during manufacture of the precursorbecame an atmosphere containing carbon dioxide gas and ammonia gasgenerated from the mixed aqueous solution rather than anoxygen-containing atmosphere.

Comparative Example 2

A precursor, a positive-electrode active material, and a secondarybattery were manufactured and evaluated in the same manner as in Example2, except that the gas injected into the reaction tank duringmanufacture of the precursor was changed to nitrogen gas. The resultingcharacteristics of the obtained precursor, positive-electrode activematerial, and secondary battery are shown in Tables 1 to 3.

Note that cross-sectional SEM observations were made on the obtainedpositive-electrode active material in the same manner as in Example 1.

FIGS. 5A and 5B show cross-sectional SEM images of representativeparticles of the positive-electrode active material. Note that FIG. 5Ashows a whole view, and FIG. 5B shows an enlarged view of a particleencircled by a dotted line in FIG. 5A.

From observing at least 100 particles, it was confirmed that the ratioof particles having porous structures with fine pores extending intotheir cores (porous particles) was 31%, and the porosity of these poroussecondary particles was 18%. Also, it was confirmed that the non-poroussecondary particles were dense particles with a porosity of no more than3%.

TABLE 1 PRECURSOR MANUFACTURING STEP PARTICLE GROWTH STEP NUCLEATIONSTEP MIXED MIXED MIXED AQUEOUS AQUEOUS AQUEOUS SOLUTION MIXED SOLUTIONMIXED SOLUTION AMMONIUM AQUEOUS AMMONIUM AQUEOUS TEMPERATURECONCENTRATION SOLUTION TIME CONCENTRATION SOLUTION (° C.) (g/L) pH (min)(g/L) pH EXAMPLE 1 40 5 6.4 100 5 7.4 EXAMPLE 2 40 5 6.4 196 5 7.4EXAMPLE 3 40 5 6.4 196 5 7.4 EXAMPLE 4 40 5 6.4 196 5 7.4 EXAMPLE 5 40 56.4 196 5 7.4 EXAMPLE 6 40 5 6.4 196 5 7.4 COMPARATIVE 40 5 6.4 110 57.4 EXAMPLE 1 COMPARATIVE 40 5 6.4 196 5 7.4 EXAMPLE 2POSITIVE-ELECTRODE ACTIVE MATERIAL MANUFACTURING STEP HEAT TREATMENTLi/Me IN FIRING TEMPERATURE LITHIUM TEMPERATURE (° C.) MIXTURE (° C.)EXAMPLE 1 500 1.5 800 EXAMPLE 2 500 1.5 800 EXAMPLE 3 500 1.5 800EXAMPLE 4 500 1.5 800 EXAMPLE 5 500 1.5 950 EXAMPLE 6 500 1.5 900COMPARATIVE 500 1.5 800 EXAMPLE 1 COMPARATIVE 500 1.5 800 EXAMPLE 2

TABLE 2 PRECURSOR COMPOSITION (at %) PRECURSOR Ni Co Mn Mo PARTICLE at %at % at % at % H/Me SPHERICALITY EXAMPLE 1 14.9 16.7 68.4 0 1.69 ◯EXAMPLE 2 15.4 16.7 67.9 0 1.66 ◯ EXAMPLE 3 14.6 16.7 67.3 1.5 1.65 ◯EXAMPLE 4 16.0 17.5 62.9 3.6 1.60 ◯ EXAMPLE 5 15.4 16.7 67.9 0 1.67 ◯EXAMPLE 6 15.4 16.7 67.9 0 1.67 ◯ COMPARATIVE 16.7 16.6 66.7 0 1.55 ◯EXAMPLE 1 COMPARATIVE 16.0 16.8 67.2 0 1.45 ◯ EXAMPLE 2

TABLE 3 ENERGY DENSITY DISCHARGE (TAP CAPACITY DENSITY × UNDER HIGHPOROUS INITIAL INITIAL DISCHARGE AVERAGE PARTICLE POROUS SPECIFICDISCHARGE DISCHARGE RATE PARTICLE NUMBER PARTICLE TAP SURFACE CAPACITYCAPACITY) CONDITION DIAMETER SPHER- RATIO POROSITY DENSITY AREA (0.05 C)(0.05 C) (2 C) (μm) ICALITY (%) (%) (g/cc) (m²/g) (mAh/g) (mAh/cc)(mAh/g) EXAMPLE 1 7.0 ◯ 100 22 1.8 12.4 282 508 216 EXAMPLE 2 7.7 ◯ 10021 1.9 12.1 282 536 213 EXAMPLE 3 7.7 ◯ 100 20 2.0 6.3 273 546 203EXAMPLE 4 6.7 ◯ 100 18 1.9 9.9 270 513 195 EXAMPLE 5 10.3 ◯ 100 23 1.71.7 295 502 200 EXAMPLE 6 10.3 ◯ 100 22 1.8 4.5 287 517 222 COMPARATIVE8.9 ◯ 58 10 2.0 6.7 233 466 135 EXAMPLE 1 COMPARATIVE 8.5 ◯ 31 18 2.03.7 204 408 92 EXAMPLE 2

It can be appreciated from Table 2 that the compositions of theprecursors of Examples 1 to 6 were all at the target composition.Further, it can be appreciated from Table 3 that the porosity of theporous particles of the positive-electrode active materials obtainedfrom the above precursors was at least 10%, and the ratio of the numberof porous particles was 100% in all of the above examples.

It was confirmed that by manufacturing a battery using suchpositive-electrode active material, the initial discharge capacity andthe discharge capacity under high discharge rate conditions of thebattery may be desirably high.

In contrast, the ratio H/Me of the precursors obtained in ComparativeExamples 1 and 2 was less than 1.6, and the compositions of theprecursors were not at the target composition. As a result, whenpositive-electrode active materials were manufactured using theseprecursors, almost no porous particles were obtained and the porosity ofthe porous particles was also reduced.

Further, it was confirmed that the initial discharge capacity and thedischarge capacity under high discharge rate conditions of the secondarybatteries manufactured using such positive-electrode active materialswere inferior to those of the secondary batteries of Examples 1 to 6.

Although the positive-electrode active material precursor for anonaqueous electrolyte secondary battery, the positive-electrode activematerial for a nonaqueous electrolyte secondary battery, the method formanufacturing a positive-electrode active material precursor for anonaqueous electrolyte secondary battery, and the method formanufacturing a positive-electrode active material for a nonaqueouselectrolyte secondary battery according to the present invention havebeen described above with respect to certain illustrative embodimentsand examples, the present invention is not limited to theabove-described embodiments and examples.

It will be apparent to those skilled in the art that variousmodifications and changes can be made without departing from the scopeof present invention.

The present application is based on and claims the benefit of priorityof Japanese Patent Application No. 2016-001366 filed on Jan. 6, 2016 andJapanese Patent Application No. 2016-186242 filed on Sep. 23, 2016, theentire contents of which are herein incorporated by reference.

1. A positive-electrode active material precursor for a nonaqueouselectrolyte secondary battery, the positive-electrode active materialprecursor comprising: a nickel-cobalt-manganese carbonate compositerepresented by general formula Ni_(x)Co_(y)Mn_(z)M_(t)CO₃ (wherex+y+z+t=1, 0.05≤x≤0.3, 0.1≤y≤0.4, 0.55≤z≤0.8, 0≤t≤0.1, and M denotes atleast one additional element selected from a group consisting of Mg, Ca,Al, Ti, V, Cr, Zr, Nb, Mo, and W); and a hydrogen-containing functionalgroup; wherein H/Me, representing a ratio of an amount of hydrogen (H)to an amount of metal components (Me) contained in thepositive-electrode active material precursor, is greater than or equalto 1.60.
 2. The positive-electrode active material precursor for anonaqueous electrolyte secondary battery according to claim 1, whereinthe additional element (M) in the general formula representing thenickel-cobalt-manganese carbonate composite includes molybdenum (Mo);and a content ratio of molybdenum (Mo) in the metal components (Me) ofthe nickel-cobalt-manganese carbonate composite is greater than or equalto 0.5 at % and less than or equal to 5 at %.
 3. A method formanufacturing a positive-electrode active material precursor for anonaqueous electrolyte secondary battery, wherein the positive-electrodeactive material precursor includes a nickel-cobalt-manganese carbonatecomposite represented by general formula Ni_(x)Co_(y)Mn_(z)M_(t)CO₃(where x+y+z+t=1, 0.05≤x≤0.3, 0.1≤y≤0.4, 0.55≤z≤0.8, 0≤t≤0.1, and Mdenotes at least one additional element selected from a group consistingof Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo, and W) and a hydrogen-containingfunctional group, the method comprising: a nucleation step of formingnuclei in a mixed aqueous solution that is prepared by mixing together,under the presence of carbonate ions, an initial aqueous solutioncontaining an alkaline substance and/or an ammonium ion supplier, anaqueous solution containing nickel as a metal component, an aqueoussolution containing cobalt as a metal component, and an aqueous solutioncontaining manganese as a metal component; and a particle growth step ofgrowing the nuclei formed in the nucleation step; wherein the nucleationstep is performed under an oxygen-containing atmosphere whilecontrolling a pH value of the mixed aqueous solution to be less than orequal to 7.5 at a reaction temperature of 40° C. as a standardtemperature.
 4. The method for manufacturing a positive-electrode activematerial precursor for a nonaqueous electrolyte secondary batteryaccording to claim 3, wherein the ammonium ion supplier is at least onesubstance selected from a group consisting of ammonium carbonate aqueoussolution, ammonia water, ammonium chloride aqueous solution, andammonium sulfate aqueous solution; and the alkaline substance is atleast one substance selected from a group consisting of sodiumcarbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide,and potassium hydroxide.
 5. The method for manufacturing apositive-electrode active material precursor for a nonaqueouselectrolyte secondary battery according to claim 3, wherein the particlegrowth step includes a step of adding and mixing into the mixed aqueoussolution obtained after the nucleation step, the aqueous solutioncontaining nickel as the metal component, the aqueous solutioncontaining cobalt as the metal component, and the aqueous solutioncontaining manganese as the metal component, under the presence ofcarbonate ions; and an ammonium ion concentration in the mixed aqueoussolution during the particle growth step is controlled to be greaterthan or equal to 0 g/L and less than or equal to 20 g/L.
 6. The methodfor manufacturing a positive-electrode active material precursor for anonaqueous electrolyte secondary battery according to claim 3, whereinthe mixed aqueous solution is maintained at a temperature greater thanor equal to 30° C. in the nucleation step.
 7. The method formanufacturing a positive-electrode active material precursor for anonaqueous electrolyte secondary battery according to claim 3, themethod further comprising: a coating step of coating the additionalelement on the positive-electrode active material precursor that hasbeen obtained in the particle growth step.
 8. The method formanufacturing a positive-electrode active material precursor for anonaqueous electrolyte secondary battery according to claim 7, whereinthe coating step is at least one step selected from a step of adding anaqueous solution containing the additional element to a slurrycontaining a suspension of the positive-electrode active materialprecursor, and causing the additional element to precipitate on asurface of the positive electrode active material precursor; a step ofspray drying a slurry containing suspensions of the positive-electrodeactive material precursor and a compound containing the additionalelement; and a step of mixing together the positive-electrode activematerial precursor and the compound containing the additional element bya solid phase method.